5-substituted-alkylaminopyrazole derivatives as pesticides

ABSTRACT

The invention relates to the use for the control of parasites in animals, of a compound which is a 5-substituted-alkylaminopyrazole derivative of formula (I) or a salt thereof: wherein the various symbols are as defined in the description, to novel 5-substituted-alkylaminopyrazole derivatives and pesticidal compositions thereof, and to processes for their preparation.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the U.S. national stage of International Appln. No.PCT/EP03/02010, filed Feb. 27, 2003, and claims the benefit under 35U.S.C. § 119(e) of United States Provisional Application No. 60/361,328,filed Mar. 5, 2002, and the priority under 35 U.S.C. § 119(a)-(d) ofEuropean Patent Appln. No. 02027033, filed Dec. 3, 2002, all of whichapplications are incorporated by reference herein in their entiretiesand relied upon.

The invention relates to the use for the control of pests (includinginsects, arachnids and helminths (including nematodes)) of5-substituted-alkylaminopyrazole derivatives, to novel compounds andcompositions used therein, and to processes used for their preparation.

The control of insects, arachnids and helminths with 1-arylpyrazolecompounds has been described in, for example, patent publication numbersWO 93/06089, WO 94/21606, WO 87/03781, EP 0295117, EP 659745, EP 679650,EP 201852 and U.S. Pat. No. 5,232,940. The control of parasites inanimals with 1-arylpyrazole compounds has also been described in, forexample, patent publication numbers WO 00/35884, EP 0846686, WO 98/24769and WO 97/28126.

In addition, WO 02/066423 describes a process for preparingI-arylpyrazole compounds.

However, the level of action and/or duration of action of theseprior-art compounds is not entirely satisfactory in all fields ofapplication, in particular against certain organisms or when lowconcentrations are applied.

Since modem pesticides must meet a wide range of demands, for exampleregarding level, duration and spectrum of action, use spectrum,toxicity, combination with other active substances, combination withformulation auxiliaries or synthesis, and since the occurrence ofresistances is possible, the development of such substances can never beregarded as concluded, and there is constantly a high. demand for novelcompounds which are advantageous over the known compounds, at least asfar as some aspects are concerned.

It was an object of the present invention to provide compounds whichwiden the spectrum of the pesticides in various aspects, specificallywith regard to the control of parasites in animals.

The present invention provides a method of controlling parasites in oron an animal comprising administering to the animal a parasiticidallyeffective amount of a 5-substituted-alkylaminopyrazole derivative offormula (I):

wherein:

-   R¹ is CN;-   W is C-halogen, C—CH₃ or N;-   R² is hydrogen, halogen or CH₃;-   R³ is (C₁-C₃)-haloalkyl, (C₁-C₃)-haloalkoxy or    S(O)_(p)—(C₁-C₃)-haloalkyl;-   R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,    (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl,    CO—(CH₂)_(q)—R⁷, COR⁸, CO—(CH₂)_(q)—R⁹,    —CO—(C₁-C₄)-alkyl-(C₁-C₆)-alkoxy, —CO₂—(CH₂)_(q)—R⁷, —CO₂R⁸,    —CO₂—(CH₂)_(q)—R⁹, —CO₂—(C₃-C₇)-cycloalkyl,    —CO₂—(C₁-C₄)-alkyl-(C₃-C₇)-cycloalkyl, —CO₂—(C₃-C₆)alkenyl,    —CO₂—(C₃-C₆)-alkynyl, CONR¹⁰R¹¹, —CH₂R⁷, —CH₂R⁹, OR⁷, OR⁸ or OR⁹; or    (C₁-C₆)-alkyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkoxy,    (C₁-C₆)-haloalkoxy, (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸,    CO₂—(C₁-C₆)-alkyl, —O(C═O)—(C₁-C₆)-alkyl, NR¹⁰COR¹², NR¹⁰R¹¹,    CONR¹⁰R¹¹, SO₂NR¹⁰OR¹¹, OH, CN, NO₂, OR⁷, NR¹⁰SO₂R⁸, COR⁸ and OR⁹;-   A is (C₁-C₁₂)-alkylene [preferably (C₁-C₆)-alkylene] or    (C₁-C₁₂)-haloalkylene [preferably (C₁-C₆)-haloalkylene] in which 2,    3 or 4 adjacent carbon atoms optionally form part of a    (C₃-C₈)-cycloalkyl ring which is unsubstituted or substituted by one    or more radicals selected from the group consisting of (C₁-C₆)-alkyl    and halogen; or is (C₁-C₁₂)-alkylene or (C₁-C₁₂)-haloalkylene in    which last two mentioned groups a methylene moiety is replaced by a    group selected from —C(═O)—, —C(═NH)—, —O—, —S— and —NR¹⁵—, with the    proviso that the replacing group is not bonded to the adjacent    S(O)_(m) group or N atom; or is (C₂-C₁₂)-alkenylene or    (C₂-C₁₂)-haloalkenylene;-   R⁵ is H, (C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl,    (C₃-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, —(CH₂)_(q)R⁷, —(CH₂)_(q)R⁹    or NR¹⁰R¹¹ provided that for the last mentioned radical m is 2; or    is (C₁-C₆)-alkyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₆)-alkenyloxy,    (C₃-C₆)-haloalkenyloxy, (C₃-C₆)-alkynyloxy, (C₃-C₆)-haloalkynyloxy,    (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CN, NO₂, OH, COR¹⁰, NR¹⁰COR¹²,    NR¹⁰SO₂R⁸, CONR¹⁰R¹¹, NR¹⁰R¹¹, S(O)_(p)R⁷, S(O)_(p)R⁹, OR⁷, OR⁹ and    CO₂R¹⁰; or-   when A is (C₁-C₁₂)-alkylene or (C₁-C₁₂)-haloalkylene and R⁵ is    (C₁-C₆)-alkyl unsubstituted or substituted by one or more halogen    radicals, one or more of the carbon atoms of R⁵ may, together with    S(O)_(m) and one or more of the carbon atoms of A, form a 5- or    6-membered ring;-   R⁶ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl,    (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl or (C₂-C₆)-haloalkynyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸, COR¹¹, COR¹³, CONR¹⁰R¹¹, SO₂NR¹⁰R¹¹, NR¹⁰R¹¹, OH, SO₃H    and (C₁-C₆)-alkylideneimino;-   R⁸ is (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,    (C₁-C₄)-haloalkoxy, NO₂, CN, CO₂(C₁-C₆)-alkyl, S(O)_(p)R⁸, OH and    oxo;-   R¹⁰ and R¹² are each independently H, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl,    (C₃-C₆)-alkynyl, (C₃-C₆)-haloalkynyl, (C₃-C₆)-cycloalkyl,    —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl, —(CH₂)_(q)R¹³ or —(CH₂)_(q)R⁹; or-   R¹⁰ and R¹¹ and/or R¹⁰ and R¹² each together with the respective    attached N atom form a five- or six-membered saturated ring which    optionally contains an additional hetero atom in the ring which is    selected from O, S and N, the ring being unsubstituted or    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₆)-alkyl and (C₁-C₆)-haloalkyl;-   R¹¹ and R¹⁴ are each independently H, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl or    —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl;-   R¹³ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸ and NR¹¹R¹⁴;-   R¹⁵ is R¹¹ or —(CH₂)_(q)R¹³;-   m, n and p are each independently zero, one or two;-   q is zero or one; and    each heterocyclyl in the above-mentioned radicals is independently a    heterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero    atoms in the ring selected from the group consisting of N, O and S;    or a pesticidally acceptable salt thereof.

In a further aspect of the invention there is provided the use ofcompounds of formula (I) and pesticidally acceptable salts thereof forthe control of parasites in and on animals.

In yet a further aspect of the invention there is provided the use ofcompounds of formula (I) and pesticidally acceptable salts thereof forpreparing a veterinary medicament, preferably for the treatment ofparasites, specifically ecto and endo parasites, in and on animals.

The invention also encompasses any stereoisomer, enantiomer or geometricisomer, and mixtures of the compounds of formula (I).

By the term “pesticidally acceptable salts” is meant salts the anions orcations of which are known and accepted in the art for the formation ofsalts for pesticidal use. Suitable salts with bases, e.g. formed bycompounds of formula (I) containing a carboxylic acid group, includealkali metal (e.g. sodium and potassium), alkaline earth metal (e.g.calcium and magnesium), ammonium and amine (e.g. diethanolamine,triethanolamine, octylamine, morpholine and dioctylmethylamine). salts.Suitable acid addition salts, e.g. formed by compounds of formula (I)containing an amino group, include salts with inorganic acids, forexample hydrochlorides, sulphates, phosphates and nitrates and saltswith organic acids for example acetic acid. In formula (I) when m is 0the term salts is understood also to include sulfonium salts, forexample alkyl or benzyl sulfonium halide salts such as the methylsulfonium chloride salts.

It is to be understood that the above mentioned provisions are includedonly for reasons of chemical instability for the particular excludedmoieties, and not for reasons of prior art.

In the present patent specification, including the accompanying claims,the aforementioned substituents have the following meanings:

Halogen atom means fluorine, chlorine, bromine or iodine.

The term “halo” before the name of a radical means that this radical ispartially or completely halogenated, that is to say, substituted by F,Cl, Br, or I, in any combination, preferably by F or Cl.

Alkyl groups and portions thereof (unless otherwise defined) may bestraight- or branched-chain.

The expression “(C₁-C₆)-alkyl” is to be understood as meaning anunbranched or branched hydrocarbon radical having 1, 2, 3, 4, 5 or 6carbon atoms, such as, for example a methyl, ethyl, propyl, isopropyl,1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical.

Alkyl radicals and also in composite groups, unless otherwise defined,preferably have 1 to 4 carbon atoms.

“(C₁-C₆)Haloalkyl” means an alkyl group mentioned under the expression“(C₁-C₆)alkyl” in which one or more hydrogen atoms are replaced by thesame number of identical or different halogen atoms, such asmonohaloalkyl, perhaloalkyl, CF₃, CHF₂, CH₂F, CHFCH₃, CF₃CH₂, CF₃CF₂,CHF₂CF₂, CH₂FCHCl, CH₂Cl, CCl₃, CHCl₂ or CH₂CH₂Cl.

The expression “(C₁-C₁₂)-alkylene” is to be understood as meaning anunbranched or branched saturated carbon chain having from 1 to 12 carbonatoms.

The expression “(C₁-C₁₂)-haloalkylene” is to be understood as meaning anunbranched or branched saturated carbon chain having from 1 to 12 carbonatoms, in which one or more hydrogen atoms are replaced by the samenumber of identical or different halogen atoms.

The expression “(C₂-C₁₂)-alkenylene” is to be understood as meaning anunbranched or branched saturated carbon chain having from 2 to 12 carbonatoms, and which contains at least one double bond which can be locatedin any position of the respective unsaturated radical.

“(C₁-C₆)Alkoxy” means an alkoxy group whose carbon chain has the meaninggiven under the expression “(C₁-C₆)alkyl”. “Haloalkoxy” is, for example,OCF₃, OCHF₂, OCH₂F, CF₃CF₂O, OCH₂CF₃ or OCH₂CH₂Cl.

“(C₂-C₆)Alkenyl” means an unbranched or branched non-cyclic carbon chainhaving a number of carbon atoms which corresponds to this stated rangeand which contains at least one double bond which can be located in anyposition of the respective unsaturated radical. “(C₂-C₆)Alkenyl”accordingly denotes, for example, the vinyl, allyl, 2-methyl-2-propenyl,2-butenyl, pentenyl, 2-methylpentenyl or the hexenyl group.

“(C₂-C₆)Alkynyl” means an unbranched or branched non-cyclic carbon chainhaving a number of carbon atoms which corresponds to this stated rangeand which contains one triple bond which can be located in any positionof the respective unsaturated radical. “(C₂-C₆)Alkynyl” accordinglydenotes, for example, the propargyl, 1-methyl-2-propynyl, 2-butynyl or3-butynyl group.

Cycloalkyl groups preferably have from three to seven carbon atoms inthe ring and are optionally substituted by halogen or alkyl.

In compounds of formula (I) the following examples of radicals areprovided:

An example of alkyl substituted by cycloalkyl is cyclopropylmethyl; anexample of alkyl substituted by alkoxy is methoxymethyl (CH₃OCH₂—); andan example of alkyl substituted by alkylthio is methylthiomethyl(CH₃SCH₂—).

A “heterocyclyl” group can be saturated, unsaturated or heteroaromatic;it preferably contains one or more, in particular 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably selected from the groupconsisting of N, O and S; it is preferably an aliphatic heterocyclylradical having 3 to 7 ring atoms or a heteroaromatic radical having 5 to7 ring atoms. The heterocyclic radical can be, for example, aheteroaromatic radical or ring (heteroaryl) such as, for example, amono-, bi- or polycyclic aromatic system in which at least 1 ringcontains one or more hetero atoms, for example pyridyl, pyrimidinyl,pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl,oxazolyl, isoxazolyl, furyl, pyrrolyl, pyrazolyl, imidazolyl andtriazolyl, or it is a partially or fully hydrogenated radical such asoxiranyl, oxetanyl, oxolanyl (=tetrahydrofuryl), oxanyl, pyrrolidyl,piperidyl, piperazinyl, dioxolanyl, oxazolinyl, isoxazolinyl,oxazolidinyl, isoxazolidinyl and morpholinyl. The “heterocyclyl” groupmay be unsubstituted or substituted by one or more radicals (preferably1, 2 or 3 radicals) selected from the group consisting of halogen,alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano,alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- anddialkylaminocarbonyl, substituted amino such as acylamino, mono- anddialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl,haloalkylsulfonyl, alkyl and haloalkyl, and additionally also oxo. Theoxo group can also be present at those hetero ring atoms where variousoxidation numbers are possible, for example in the case of N and S.

The term pests means arthropod pests (including insects and arachnids),and helminths (including nematodes). The term parasites embraces allpests that live in or on animals.

A preferred class of compounds of formula (I) for use in the inventionare those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is hydrogen or halogen;-   R³ is CF₃or OCF₃;-   R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,    (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, CO₂R⁸,    —CH₂R⁷, —CH₂R⁹, OR⁷, OR⁸ or OR⁹; or (C₁-C₆)-alkyl unsubstituted or    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl;-   A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene, in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₆)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₆)-cycloalkyl, —(CH₂)_(q)R⁷; or (C₁-C₆)-alkyl    unsubstituted or substituted by one or more radicals selected from    the group consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl; or when A is    (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl and R⁵ is (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl, one or more of the carbon atoms of the R⁵ group    may, together with the S(O)_(m) group and one or more of the carbon    atoms of A, form a 5- or 6-membered ring;-   R⁶ and R⁸ are each independently (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹¹R¹²;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl and (C₁-C₄)-alkoxy;-   R¹¹ and R¹² are each the same or different hydrogen, (C₁-C₆)-alkyl    or (C₁-C₆)-haloalkyl;-   m, n and p are each independently zero, one or two; and-   q is zero or one.

Another preferred class of compounds of formula (I) for use in theinvention are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl,    (C₃-C₇)-cycloalkyl, —CO₂—(C₁-C₃)-alkyl, —CO₂—(C₃-C₆)-cycloalkyl,    —CO₂—(C₁-C₃)-alkyl-(C₃-C₆)-cycloalkyl, —CH₂R⁷ or —CH₂R⁹; or    (C₁-C₄)-alkyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₃)-alkoxy,    (C₁-C₃)-haloalkoxy, (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸,    CO₂—(C₁-C₃)-alkyl, —O(C═O)—(C₁-C₃)-alkyl, NR¹⁰R¹¹, OH, CN, NO₂, OR⁷    or OR⁹;-   A is (C₁-C₉)-alkylene or (C₁-C₉)-haloalkylene in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₈)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₇)-cycloalkyl or —(CH₂)_(q)R⁷; or is (C₁-C₆)-alkyl    unsubstituted or substituted by one or more radicals selected from    the group consisting of halogen, (C₁-C₃)-alkoxy, (C₁-C₄)-haloalkoxy,    (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CN, NR¹⁰R¹¹, S(O)_(p)R⁷, S(O)_(p)R⁹,    OR⁷ and OR⁹;-   R⁶ is (C₁-C₂)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₄)-alkyl,    (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸, COR¹¹, NR¹⁰R¹¹ and OH;-   R⁸ is (C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl and (C₁-C₄)-alkoxy;-   R¹⁰ is H, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₃-C₄)-alkenyl,    (C₃-C₄)-alkynyl, (C₃-C₆)-cycloalkyl,    —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl or —(CH₂)_(q)R¹³; or-   R¹⁰ and R¹¹ together with the attached N atom form a five- or    six-membered saturated ring which optionally contains an additional    hetero atom in the ring which is selected from O, S and N, the ring    being unsubstituted or substituted by one or more radicals selected    from the group consisting of halogen and (C₁-C₃)-alkyl;-   R¹¹ and R¹⁴ are each independently H, (C₁-C₃)-alkyl,    (C₁-C₃)-haloalkyl, (C₃-C₆)-cycloalkyl or    —(C₁-C₃)-alkyl-(C₃-C₆)-cycloalkyl;-   R¹³ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₃)-alkyl,    (C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸ and NR¹¹R¹⁴;-   m, n and p are each independently zero, one or two;-   q is zero or one; and-   each heterocyclyl in the above-mentioned radicals is independently a    heteroaromatic radical having 5 or 6 ring atoms and 1, 2 or 3 hetero    atoms in the ring selected from the group consisting of N, O and S.

A further preferred class of compounds of formula (I) for use in theinvention are those in which:

-   R¹ is CN;-   W is C—Cl;-   R² is chlorine;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, CO₂—(C₁-C₃)-alkyl, or (C₁-C₆)-alkyl unsubstituted or    substituted by one or more radicals selected from the group    consisting of halogen and (C₁-C₃)-alkoxy;-   A is (C₁-C₄)-alkylene;-   R⁵ is (C₃-C₆)-cycloalkyl, —(CH₂)_(q)R⁷, (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl; or when R⁵ is (C₁-C₆)-alkyl, one or more of the    carbon atoms of the R⁵ group may, together with the S(O)_(m) group    and one or more of the carbon atoms of A, form a 5- or 6-membered    ring;-   R⁶ is CF₃, CF₂Cl, CFCl₂, CBrF₂ or CHF₂;-   R⁷ is phenyl;-   m and n are each independently zero, one or two; and-   q is zero or one.

A further preferred class of compounds of formula (I) for use in theinvention are those in which:

-   R¹ is CN;-   W is C—Cl;-   R² is Cl;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl,    (C₃-C₇)-cycloalkyl, COR⁹ (where R⁹ is tetrahydrofuryl),    —COCH₂—(C₁-C₆)-alkoxy, —CO₂—(C₁-C₆)-alkyl, —CO₂—(CH₂)_(q)—R⁷, OR⁷,    OR⁸ or OR⁹ (where R⁹ is pyridyl); or C₁-C₆)-alkyl unsubstituted or    substituted by one or more radicals selected from the group    consisting of (C₁-C₆)-alkoxy, (C₃-C₇)-cycloalkyl and S(O)_(p)R⁸;-   A is (C₁-C₆)-alkylene in which 2, 3 or 4 adjacent carbon atoms    optionally form part of a (C₃-C₆)-cycloalkyl ring;-   R⁵ is (C₃-C₆)-alkenyl, (C₃-C₇)-cycloalkyl, —(CH₂)_(q)R⁷ or NR¹⁰R¹¹    provided that for the last mentioned radical X is SO₂; or is    (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁶ is CF₃, CF₂Cl, CFCl₂, CBrF₂, CHF₂ or CH₃;-   R⁷ is phenyl unsubstituted or substituted by one or more    (C₁-C₆)-alkoxy groups;-   R⁸ is (C₁-C₆)-alkyl;-   R¹⁰ and R¹¹ are the same or different (C₁-C₆)-alkyl; or-   R¹⁰ and R¹¹ together with the attached N atom form a five- or    six-membered saturated ring which optionally contains an additional    hetero atom in the ring which is selected from O, S and N;-   m and n are each independently zero, one or two; and-   q is zero or one.

Another preferred class of compounds of formula (I) for use in theinvention are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is hydrogen or halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,    (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₃-C₆)-cycloalkyl,    —CO₂—(C₁-C₆)-alkyl or —CH₂R⁷; or (C₁-C₆)-alkyl unsubstituted or    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl;-   A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₆)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₆)-cycloalkyl or —(CH₂)_(q)R⁷; or is (C₁-C₆)-alkyl    unsubstituted or substituted by one or more radicals selected from    the group consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl; or-   when A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene and R⁵ is    (C₁-C₆)-alkyl unsubstituted or substituted by one or more halogen    radicals, one or more of the carbon atoms of R⁵ may, together with    S(O)_(m) and one or more of the carbon atoms of A, form a 5- or    6-membered ring;-   R⁶ and R⁸ are each independently (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)alkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹⁰R¹¹;-   R¹⁰ and R¹¹ are each independently H, (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl;-   m, n and p are each independently zero, one or two; and-   q is zero or one.

A further preferred class of compounds of formula (I) for use in theinvention are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,    (C₃-C₇)-cycloalkyl, (C₁-C₄)-alkyl-(C₃-C₇)-cycloalkyl,    —CO₂—(C₁-C₆)-alkyl, (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   A is (C₁-C₁₂)-alkylene which is unsubstituted or substituted by one    or more radicals selected from the group consisting of (C₁-C₆)-alkyl    and halogen;-   R⁵ is (C₁-C₆)-alkyl;-   R⁶ is CF₃, CF₂Cl, CFCl₂, CBrF₂ or CHF₂; and-   m and n are each independently zero, one or two.

Further especially preferred classes of compounds of formula (I) for usein the invention are those in which one or more of the followingfeatures are present:

-   R⁴ is hydrogen, (C₁-C₄)-alkyl, —CO₂—(C₁-C₄)-alkyl, (C₃-C₄)-alkenyl,    (C₁-C₂)-alkyl-(C₃-C₄)-cycloalkyl or (C₃-C₄)-cycloalkyl;-   R⁵ is (C₁-C₂)-alkyl; and-   A is (C₂-C₃)-alkylene.

Another especially preferred class of compounds for use in the inventionare those wherein:

-   R¹ is CN;-   R² is chlorine;-   R³ is CF₃;-   W is C—Cl;-   R⁴ is hydrogen, (C₁-C₄)-alkyl, —CO₂—(C₁-C₄)-alkyl, (C₃-C₄)-alkenyl,    (C₁-C₂)-alkyl-(C₃-C₄)-cycloalkyl, or (C₃-C₄)-cycloalkyl;-   R⁵ is (C₁-C₂)-alkyl;-   R⁶ is CF₃;-   A is (C₂-C₃)-alkylene; and-   m and n are each independently zero, one or two.

A more preferred class of compounds of formula (I) for use in theinvention are those in which:

-   R¹ is CN; R² is chlorine; R³ is CF₃ or OCF₃; W is C—Cl; R⁴ is    hydrogen or (C₁-C₆)-alkyl; R⁵ is (C₁-C₆)-alkyl; R⁶ is CF₃; A is    (C₁-C₄)-alkylene and m and n are each independently zero, one or    two.

Further especially preferred classes of compounds of formula (I) for usein the invention are those wherein one or more of the following featuresare present:

-   W is C—Cl;-   R² is chlorine;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁵ is (C₁-C₆)-alkyl;-   R⁶ is (C₁-C₃)-haloalkyl (R⁶ is more preferably CF₃); and/or-   A is (C₁-C₆)-alkylene (more preferably A is (C₂-C₃)-alkylene).

Some of the compounds of formula (I) are new and a further feature ofthe present invention is therefore directed to the novel compounds offormula (I).

One class of novel 5-substituted-alkylaminopyrazole derivatives offormula (I), or pesticidally acceptable salts thereof, are thosewherein:

-   R¹ is CN;-   W is C-halogen or C—CH₃;-   R² is hydrogen, halogen or CH₃;-   R³ is (C₁-C₃)-haloalkyl, (C₁-C₃)-haloalkoxy or    S(O)_(p)—(C₁-C₃)-haloalkyl;-   R⁴ is (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl,    (C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, CO—(CH₂)_(q)—R⁷,    CO—(CH₂)_(q)—R⁹, —CO—(C₁-C₄)-alkyl-(C₁-C₆)-alkoxy,    —CO₂—(CH₂)_(q)—R⁷, —CO₂R⁸, —CO₂—(CH₂)_(q)—R⁹,    —CO₂—(C₃-C₇)-cycloalkyl, —CO₂—(C₁-C₄)-alkyl-(C₃-C₇)-cycloalkyl,    —CO₂—(C₃-C₆)-alkenyl, —CO₂—(C₃-C₆)-alkynyl, CONR¹⁰R¹¹, —CH₂R⁷,    —CH₂R⁹, OR⁷, OR⁸ or OR⁹; or (C₁-C₆)-alkyl which is substituted by    one or more radicals selected from the group consisting of halogen,    (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸,    CO₂—(C₁-C₆)-alkyl, —O(C═O)—(C₁-C₆)-alkyl, NR¹⁰COR¹², NR¹⁰R¹¹,    CONR¹⁰R¹¹, SO₂NR¹⁰R¹¹, OH, CN, NO₂, OR⁷, NR¹⁰SO₂R⁸, COR⁸ and OR⁹;-   A is (C₁-C₁₂)-alkylene [preferably C₁-C₆)-alkylene] and    (C₁-C₁₂)-haloalkylene [preferably (C₁-C₆)-haloalkylene] in which 2,    3 or 4 adjacent carbon atoms optionally form part of a    (C₃-C₈)-cycloalkyl ring which is unsubstituted or substituted by one    or more radicals selected from the group consisting of (C₁-C₆)-alkyl    and halogen; or is (C₁-C₁₂)-alkylene or (C₁-C₁₂)-haloalkylene in    which last two mentioned groups a methylene moiety is replaced by a    group selected from —C(═O)—, —C(═NH)—, —O—, —S— and —NR¹⁵—, with the    proviso that the replacing group is not bonded to the adjacent    S(O)_(m) group or N atom; or is (C₂-C₁₂)-alkenylene or    (C₂-C₁₂)-haloalkenylene;-   R⁵ is H, (C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl,    (C₃-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, —(CH₂)_(q)R⁷, —(CH₂)_(q)R⁹    or NR¹⁰R¹¹ provided that for the last mentioned radical m is 2; or    is (C₁-C₆)-alkyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₆)-alkenyloxy,    (C₃-C₆)-haloalkenyloxy, (C₃-C₆)-alkynyloxy, (C₃-C₆)-haloalkynyloxy,    (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CN, NO₂, OH, COR¹⁰, NR¹⁰COR₁₂,    NR¹⁰SO₂R⁸, CONR¹⁰R¹¹, NR¹⁰R¹¹, S(O)_(p)R⁷, S(O)_(p)R⁹, OR⁷, OR⁹ and    CO₂R¹⁰; or-   when A is (C₁-C₁₂)-alkylene or (C₁-C₁₂)-haloalkylene and R⁵ is    (C₁-C₆)-alkyl unsubstituted or substituted by one or more halogen    radicals, one or more of the carbon atoms of R⁵ may, together with    S(O)_(m) and one or more of the carbon atoms of A, form a 5- or    6-membered ring;-   R⁶ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl,    (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl or (C₂-C₆)-haloalkynyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸, COR¹¹, COR¹³, CONR¹⁰R¹¹, SO₂NR¹⁰R¹¹, NR¹⁰R¹¹, OH, SO₃H    and (C₁-C₆)-alkylideneimino;-   R⁸ is (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,    (C₁-C₄)-haloalkoxy, NO₂, CN, CO₂(C₁-C₆)-alkyl, S(O)_(p)R⁸, OH and    oxo;-   R¹⁰ and R¹² are each independently H, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl,    (C₃-C₆)-alkynyl, (C₃-C₆)-haloalkynyl, (C₃-C₆)-cycloalkyl,    —(C₁-C₆)-alkyl-(C₃-C₆)cycloalkyl, —(CH₂)_(q)R¹³ or —(CH₂)_(q)R⁹; or-   R¹⁰ and R¹¹ and/or R¹⁰ and R¹² each together with the respective    attached N atom form a five- or six-membered saturated ring which    optionally contains an additional hetero atom in the ring which is    selected from O, S and N, the ring being unsubstituted or    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₆)-alkyl and (C₁-C₆)-haloalkyl;-   R¹¹ and R¹⁴ are each independently H, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl or    —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl;-   R¹³ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸ and NR¹¹R¹⁴;-   R¹⁵ is R¹¹ or —(CH₂)_(q)R¹³;-   m, n and p are each independently zero, one or two;-   q is zero or one; and-   each heterocyclyl in the above-mentioned radicals is independently a    heterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero    atoms in the ring selected from the group consisting of N, O and S.

A preferred class of compounds of formula (I) are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is hydrogen or halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl,    (C₂-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, CO₂R⁸,    —CO₂—(C₃-C₆)-alkenyl, —CO₂—(C₃-C₆)-alkynyl, —CO2—CH₂R⁷, —CH₂R⁹, OR⁷,    OR⁸ or OR⁹; or (C₁-C₆)-alkyl which is substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₇)cycloalkyl, S(O)_(p)R⁸    and CO₂—(C₁-C₆)-alkyl;-   A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene, in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₆)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₆)-cycloalkyl, —(CH₂)_(q)R⁷; or (C₁-C₆)-alkyl    unsubstituted or substituted by one or more radicals selected from    the group consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)alkyl; or when A is    (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl and R⁵ is (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl, one or more of the carbon atoms of the R⁵ group    may, together with the S(O)_(m) group and one or more of the carbon    atoms of A, form a 5- or 6-membered ring;-   R⁶ and R⁸ are each independently (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹¹R¹²;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl and (C₁-C₄)-alkoxy;-   R¹¹ and R¹² are each the same or different hydrogen, (C₁-C₆)-alkyl    or (C₁-C₆)-haloalkyl;-   m, n and p are each independently zero, one or two; and-   q is zero or one.

Another preferred class of compounds of formula (I) are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is hydrogen or halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl,    (C₂-C₆)-haloalkynyl, (C₃-C₆)-cycloalkyl, CO₂R⁸,    —CO₂—(C₃-C₆)-alkynyl, or —CH₂R⁷; or (C₁-C₆)-alkyl which is    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl;-   A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₆)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₆)-cycloalkyl or —(CH₂)_(q)R⁷; or is (C₁-C₆)-alkyl    unsubstituted or substituted by one or more radicals selected from    the group consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl; or-   when A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene and R⁵ is    (C₁-C₆)-alkyl unsubstituted or substituted by one or more halogen    radicals, one or more of the carbon atoms of R⁵ may, together with    S(O)_(m) and one or more of the carbon atoms of A, form a 5- or    6-membered ring;-   R⁶ and R⁸ are each independently (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹⁰R¹¹;-   R¹⁰ and R¹¹ are each independently H, (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl;-   m, n and p are each independently zero, one or two; and-   q is zero or one.

Another preferred class of compounds of formula (I) are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₃-C₇)-cycloalkyl, —CO₂R⁸,    —CO₂—(C₃-C₆)-alkynyl, —CO₂—(C₃-C₆)-cycloalkyl,    —CO₂—(C₁-C₃)-alkyl-(C₃-C₆)-cycloalkyl, —CH₂R⁷ or —CH₂R⁹; or    (C₁-C₄)-alkyl which is substituted by one or more radicals selected    from the group consisting of halogen, (C₁-C₃)-alkoxy,    (C₁-C₃)-haloalkoxy, (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸,    CO₂—(C₁-C₃)-alkyl, —O(C═O)—(C₁-C₃)-alkyl, NR¹⁰R¹¹, OH, CN, NO₂, OR⁷    or OR⁹;-   A is (C₁-C₉)-alkylene or (C₁-C₉)-haloalkylene in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₈)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₇)-cycloalkyl or —(CH₂)_(q)R⁷; or is (C₁-C₆)-alkyl    unsubstituted or substituted by one or more radicals selected from    the group consisting of halogen, (C₁-C₃)-alkoxy, (C₁-C₄)-haloalkoxy,    (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CN, NR¹⁰R¹¹, S(O)_(p)R⁷, S(O)_(p)R⁹,    OR⁷ and OR⁹;-   R⁶ is (C₁-C₂)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₄)-alkyl,    (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸, COR¹¹, NR¹⁰R¹¹ and OH;-   R⁸ is (C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl and (C₁-C₄)-alkoxy;-   R¹⁰ is H, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₃-C₄)-alkenyl,    (C₃-C₄)-alkynyl, (C₃-C₆)-cycloalkyl, —(C₁-C₆)-alkyl-(C₃-C₆cycloalkyl    or —(CH₂)_(q)R¹³; or-   R¹⁰ and R¹¹ together with the attached N atom form a five- or    six-membered saturated ring which optionally contains an additional    hetero atom in the ring which is selected from O, S and N, the ring    being unsubstituted or substituted by one or more radicals selected    from the group consisting of halogen and (C₁-C₃)-alkyl;-   R¹¹ and R¹⁴ are each independently H, (C₁-C₃)-alkyl,    (C₁-C₃)-haloalkyl, (C₃-C₆)-cycloalkyl or    —(C₁-C₃)-alkyl-(C₃-C₆)-cycloalkyl;-   R¹³ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₃)-alkyl,    (C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸ and NR¹¹R¹⁴;-   m, n and p are each independently zero, one or two;-   q is zero or one; and-   each heterocyclyl in the above-mentioned radicals is independently a    heteroaromatic radical having 5 or 6 ring atoms and 1, 2 or 3 hetero    atoms in the ring selected from the group consisting of N, O and S.

A further preferred class of compounds of formula (I) are those inwhich:

-   R¹ is CN;-   W is C—Cl;-   R² is chlorine;-   R³ is CF₃ or OCF₃;-   R⁴ is CO₂—(C₁-C₃)-alkyl, or (C₁-C₆)-alkyl which is substituted by    one or more radicals selected from the group consisting of halogen    and (C₁-C₃)-alkoxy;-   A is (C₁-C₄)-alkylene;-   R⁵ is (C₃-C₆)-cycloalkyl, —(CH₂)_(q)R⁷, (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl; or when R⁵ is (C₁-C₆)-alkyl, one or more of the    carbon atoms of the R⁵ group may, together with the S(O)_(m) group    and one or more of the carbon atoms of A, form a 5- or 6-membered    ring;-   R⁶ is CF₃, CF₂Cl, CFCl₂, CBrF₂ or CHF₂;-   R⁷ is phenyl;-   m and n are each independently zero, one or two; and-   q is zero or one.

A further preferred class of compounds of formula (I) are those inwhich:

-   R¹ is CN;-   W is C-halogen;-   R² is halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₃-C₇)-cycloalkyl,    (C₁-C₄)-alkyl-(C₃-C₇)-cycloalkyl, —CO₂—(C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl;-   A is (C₁-C₁₂)-alkylene which is unsubstituted or substituted by one    or more radicals selected from the group consisting of (C₁-C₆)-alkyl    and halogen;-   R⁵ is (C₁-C₆)-alkyl;-   R⁶ is CF₃, CF₂Cl, CFCl₂, CBrF₂ or CHF₂; and-   m and n are each independently zero, one or two.

An especially preferred class of compounds of formula (I) are thosewherein:

-   R¹ is CN;-   R² is chlorine;-   R³ is CF₃;-   W is C—Cl;-   R⁴ is —CO₂—(C₁-C₄)-alkyl, (C₃-C₄)-alkenyl,    (C₁-C₂)-alkyl-(C₃-C₄)-cycloalkyl or (C₃-C₄)-cycloalkyl (more    preferably R⁴ is —CO₂—(C₁-C₄)-alkyl);-   R⁵ is (C₁-C₂)-alkyl;-   R⁶ is CF₃;-   A is (C₂-C₃)-alkylene; and-   m and n are each independently zero, one or two.

Another class of novel 5-substituted-alkylaminopyrazole derivatives offormula (I), or a pesticidally acceptable salt thereof, are thosewherein:

-   R¹ is CN;-   W is C-halogen or C—CH₃;-   R² is hydrogen, halogen or CH₃;-   R³ is (C₁-C₃)-haloalkyl, (C₁-C₃)-haloalkoxy or    S(O)_(p)—(C₁-C₃)-haloalkyl;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or COR⁸;-   A is (C₁-C₁₂)-alkylene [preferably (C₁-C₆)-alkylene] and    (C₁-C₁₂)-haloalkylene [preferably (C₁-C₆)-haloalkylene] in which 2,    3 or 4 adjacent carbon atoms optionally form part of a    (C₃-C₈)-cycloalkyl ring which is unsubstituted or substituted by one    or more radicals selected from the group consisting of (C₁-C₆)-alkyl    and halogen; or is (C₁-C₁₂)-alkylene or (C₁-C₁₂)-haloalkylene in    which last two mentioned groups a methylene moiety is replaced by a    group selected from —C(═O)—, —C(═NH)—, —O—, —S— and —NR¹⁵—, with the    proviso that the replacing group is not bonded to the adjacent    S(O)_(m) group or N atom; or is (C₂-C₁₂)-alkenylene or    (C₂-C₁₂)-haloalkenylene;-   R⁵ is H, (C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl,    (C₃-C₆)-haloalkynyl, (C₃-C₇)-cycloalkyl, —(CH₂)_(q)R⁷, —(CH₂)_(q)R⁹    or NR¹⁰R¹¹ provided that for the last mentioned radical S(O)_(m) is    SO₂; or is (C₁-C₆)-alkyl substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkoxy,    (C₁-C₆)-haloalkoxy, (C₃-C₆)-alkenyloxy, (C₃-C₆)-haloalkenyloxy,    (C₃-C₆)-alkynyloxy, (C₃-C₆)-haloalkynyloxy, (C₃-C₇)-cycloalkyl,    S(O)_(p)R⁸, CN, NO₂, OH, COR¹⁰, NR¹⁰COR¹², NR¹⁰SO₂R⁸, CONR¹⁰R¹¹,    NR¹⁰R¹¹, S(O)_(p)R⁷, S(O)_(p)R⁹, OR⁷, OR⁹ and CO₂R¹⁰; or-   when A is (C₁-C₁₂)-alkylene or (C₁-C₁₂)-haloalkylene and R⁵ is    (C₁-C₆)-alkyl substituted by one or more halogen radicals, one or    more of the carbon atoms of R⁵ may, together with S(O)_(m) and one    or more of the carbon atoms of A, form a 5- or 6-membered ring;-   R⁶ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl,    (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl or (C₂-C₆)-haloalkynyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸, COR¹¹, COR¹³, CONR¹⁰R¹¹, SO₂NR¹⁰R¹¹, NR¹⁰R¹¹, OH, SO₃H    and (C₁-C₆)-alkylideneimino;-   R⁸ is (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,    (C₁-C₄)-haloalkoxy, NO₂, CN, CO₂(C₁-C₆)-alkyl, S(O)_(p)R⁸, OH and    oxo;-   R¹⁰ and R¹² are each independently H, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl,    (C₃-C₆)-alkynyl, (C₃-C₆)-haloalkynyl, (C₃-C₆)-cycloalkyl,    —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl, —(CH₂)_(q)R¹³ or —(CH₂)_(q)R⁹; or-   R¹⁰ and R¹¹ and/or R¹⁰ and R¹² each together with the respective    attached N atom form a five- or six-membered saturated ring which    optionally contains an additional hetero atom in the ring which is    selected from O, S and N, the ring being unsubstituted or    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₆)-alkyl and (C₁-C₆)-haloalkyl;-   R¹¹ and R¹⁴ are each independently H, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl or    —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl;-   R¹³ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸ and NR¹¹R¹⁴;-   R¹⁵ is R¹¹ or —(CH₂)_(q)R¹³;-   m, n and p are each independently zero, one or two;-   q is zero or one; and-   each heterocyclyl in the above-mentioned radicals is independently a    heterocyclic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero    atoms in the ring selected from the group consisting of N, O and S.

A preferred class of compounds of formula (I) are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is hydrogen or halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or COR⁸;-   A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene, in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₆)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₆)-cycloalkyl, —(CH₂)_(q)R⁷; or (C₁-C₆)-alkyl substituted    by one or more radicals selected from the group consisting of    halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₆)-cycloalkyl,    S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl; or when A is (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl and R⁵ is (C₁-C₆)-haloalkyl, one or more of the    carbon atoms of the R⁵ group may, together with the S(O)_(m) group    and one or more of the carbon atoms of A, form a 5- or 6-membered    ring;-   R⁶ and R⁸ are each independently (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹¹R¹²;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl and (C₁-C₄)-alkoxy;-   R¹¹ and R¹² are each the same or different hydrogen, (C₁-C₆)-alkyl    or (C₁-C₆)-haloalkyl;-   m, n and p are each independently zero, one or two; and-   q is zero or one.

Another preferred class of compounds of formula (I) are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is hydrogen or halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or COR⁸;-   A is (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₆)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₆)-cycloalkyl or —(CH₂)_(q)R⁷; or is (C₁-C₆)-alkyl    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,    (C₃-C₆)-cycloalkyl, S(O)_(p)R⁸ and CO₂—(C₁-C₆)-alkyl; or when A is    (C₁-C₆)-alkylene or (C₁-C₆)-haloalkylene and R⁵ is (C₁-C₆)-alkyl    substituted by one or more halogen radicals, one or more of the    carbon atoms of R⁵ may, together with S(O)_(m) and one or more of    the carbon atoms of A, form a 5- or 6-membered ring;-   R⁶ and R⁸ are each independently (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₆)-alkyl,    (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹⁰R¹¹;-   R¹⁰ and R¹¹ are each independently H, (C₁-C₆)-alkyl or    (C₁-C₆)-haloalkyl;-   m, n and p are each independently zero, one or two; and-   q is zero or one.

Another preferred class of compounds of formula (I) are those in which:

-   R¹ is CN;-   W is C-halogen;-   R² is halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or COR⁸;.-   A is (C₁-C₉)-alkylene or (C₁-C₉)-haloalkylene in which 2, 3 or 4    adjacent carbon atoms optionally form part of a (C₃-C₈)-cycloalkyl    ring which is unsubstituted or substituted by one or more radicals    selected from the group consisting of (C₁-C₆)-alkyl and halogen;-   R⁵ is (C₃-C₇)-cycloalkyl or —(CH₂)_(q)R⁷; or is (C₁-C₆)-alkyl    substituted by one or more radicals selected from the group    consisting of halogen, (C₁-C₃)-alkoxy, (C₁-C₄)-haloalkoxy,    (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CN, NR¹⁰R¹¹ and S(O)_(p)R⁷;-   R⁶ is (C₁-C₂)-haloalkyl;-   R⁷ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₄)-alkyl,    (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸, COR¹¹, NR¹⁰R¹¹ and OH;-   R⁸ is (C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl;-   R⁹ is heterocyclyl unsubstituted or substituted by one or more    radicals selected from the group consisting of halogen,    (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl and (C₁-C₄)-alkoxy;-   R¹⁰ is H, (C₁-C₃)-alkyl, (C₁-C₃)-haloalkyl, (C₃-C₄)-alkenyl,    (C₃-C₄)-alkynyl, (C₃-C₆)-cycloalkyl,    —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl or —(CH₂)_(q)R¹³; or-   R¹⁰ and R¹¹ together with the attached N atom form a five- or    six-membered saturated ring which optionally contains an additional    hetero atom in the ring which is selected from O, S and N, the ring    being unsubstituted or substituted by one or more radicals selected    from the group consisting of halogen and (C₁-C₃)-alkyl;-   R¹¹ and R¹⁴ are each independently H, (C₁-C₃)-alkyl,    (C₁-C₃)-haloalkyl, (C₃-C₆)-cycloalkyl or    —(C₁-C₃)-alkyl-(C₃-C₆)-cycloalkyl;-   R¹³ is phenyl unsubstituted or substituted by one or more radicals    selected from the group consisting of halogen, (C₁-C₃)-alkyl,    (C₁-C₃)-haloalkyl, (C₁-C₃)-alkoxy, (C₁-C₃)-haloalkoxy, CN, NO₂,    S(O)_(p)R⁸ and NR¹¹R¹⁴;-   m, n and p are each independently zero, one or two;-   q is zero or one; and-   each heterocyclyl in the above-mentioned radicals is independently a    heteroaromatic radical having 5 or 6 ring atoms and 1, 2 or 3 hetero    atoms in the ring selected from the group consisting of N, O and S.

A further preferred class of compounds of formula (I) are those inwhich:

-   R¹ is CN;-   W is C—Cl;-   R² is chlorine;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or COR⁸;-   A is (C₁-C₄)-alkylene;-   R⁵ is (C₃-C₆)-cycloalkyl, —(CH₂)_(q)R⁷ or (C₁-C₆)-haloalkyl; or when    R⁵ is (C₁-C₆)-haloalkyl, one or more of the carbon atoms of the R⁵    group may, together with the S(O)_(m) group and one or more of the    carbon atoms of A, form a 5- or 6-membered ring;-   R⁶ is CF₃, CF₂Cl, CFCl₂, CBrF₂ or CHF₂;-   R⁷ is phenyl;-   m and n are each independently zero, one or two; and-   q is zero or one.

A further preferred class of compounds of formula (I) are those inwhich:

-   R¹ is CN;-   W is C-halogen;-   R² is halogen;-   R³ is CF₃ or OCF₃;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or COR⁸;-   A is (C₁-C₁₂)-alkylene which is unsubstituted or substituted by one    or more radicals selected from the group consisting of (C₁-C₆)-alkyl    and halogen;-   R⁵ is (C₁-C₆)-haloalkyl;-   R⁶ is CF₃, CF₂Cl, CFCl₂, CBrF₂ or CHF₂; and-   m and n are each independently zero, one or two.

An especially preferred class of compounds of formula (I) are thosewherein:

-   R¹ is CN;-   R² is chlorine;-   R³ is CF₃;-   W is C—Cl;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or COR⁸;-   R⁵ is (C₁-C₂)-haloalkyl;-   R⁶ is CF₃;-   A is (C₂-C₃)-alkylene; and-   m and n are each independently zero, one or two.

Yet another class of novel 5-substituted-alkylaminopyrazole derivativesof formula (I), or a pesticidally acceptable salt thereof, are thosewherein:

-   R¹ is CN; R² is chlorine; R³ is CF₃ or OCF₃; W is C—Cl; R⁴ is    hydrogen or (C₁-C₆)-alkyl; R⁵ is C₁-C₆)-alkyl; R⁶ is CF₃; A is    (C₁-C₄)-alkylene (preferably A is (C₂-C₃)-alkylene) and m and n are    each independently zero, one or two.

A further particularly preferred embodiment of the invention relates tonovel 5-substituted-alkylaminopyrazole derivatives of formula (I), orpesticidally acceptable salts thereof, wherein:

-   R¹ is CN;-   W is C—Cl;-   R² is chlorine;-   R³ is CF₃;-   R⁴ is hydrogen or (C₁-C₃)-alkyl (more preferably R⁴ is hydrogen or    methyl);-   A is —CH₂—CH₂— or —CH₂CH₂CH₂—;-   R⁵ is (C₁-C₄)-alkyl (more preferably R⁵ is (C₁-C₂)-alkyl, most    preferably R⁵ is methyl);-   R⁶ is CF₃; and-   m and n are each independently zero, one or two.

The compounds of general formula (I) can be prepared by the applicationor adaptation of known methods (i.e. methods heretofore used ordescribed in the chemical literature.

In the following description of processes when symbols appearing informulae are not specifically defined, it is understood that they are“as defined above” in accordance with the first definition of eachsymbol in the specification.

According to a feature of the invention compounds of formula (I) whereinR¹, R², R³, R⁶, W, A and n are as defined above, R⁴ and R⁵ are asdefined above with the exclusion of hydrogen, and R⁴ is H, may beprepared by the reaction of a compound of formula (II):

wherein R¹, R², R³, R⁶, W and n are as defined above and L is a leavinggroup, generally halogen and preferably bromine, with a compound offormula (III):R⁵—S(O)_(m)-A-NH₂  (III)wherein A and m are as defined above and R⁵ is as defined above with theexclusion of hydrogen. The reaction is generally performed in thepresence of a base such an alkali metal carbonate, for example potassiumcarbonate, in a solvent such as dioxan, tetrahydrofuran orN,N-dimethylformamide, at a temperature of from 0° to 100° C.(preferably 0° to 50° C.).

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁴, R⁶, W, A, m and n are as defined above and R⁴ isas defined above with the exclusion of hydrogen, OR⁷, OR⁸ and OR⁹, R⁵ isas defined above with the exclusion of H, may also be prepared by thealkylation or acylation of a corresponding compound of formula (IV):

wherein R¹, R², R³, R⁶, W, A, m and n are as defined above and R⁵ is asdefined above with the exclusion of hydrogen, with a compound of formula(V):R⁴-L¹  (V)wherein R⁴ is as defined above with the exclusion of hydrogen, OR⁷, OR⁸and OR⁹, and L¹ is a leaving group, generally halogen and preferablychlorine or iodine in the case of alkylation reactions, or preferablychlorine for acylations. The reaction is generally performed in thepresence of a base such as sodium hydride, in a solvent such as dioxan,tetrahydrofuran or N,N-dimethylformamide, at a temperature of from 0° to100° C. (preferably 0° to 50° C.).

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁴, R⁶, W, A, m and n are as defined above and R⁵ isas defined above with the exclusion of hydrogen, may also be prepared bythe reaction of a compound of formula (VI):

wherein R¹, R², R³, R⁴, R⁶, W and n are as defined above, with acompound of formula (VII):R⁵—S(O)_(m)-A-L²  (VII)wherein m and A are as defined above, R⁵ is as defined above with theexclusion of hydrogen and L² is a leaving group, generally halogen andpreferably chlorine. The reaction is generally performed in the presenceof a base such sodium hydride, in a solvent such as dioxan,tetrahydrofuran or N,N-dimethylformamide, at a temperature of from 0° to100° C. (preferably 0° to 50° C.).

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁶, W, m and n are as defined above, R⁵ is asdefined above with the exclusion of hydrogen, R⁴ is hydrogen; m is 0 andA is —CH₂—, may be prepared by the reaction of a compound of formula(VIII):

wherein R¹, R², R³, R⁶, W and n are as defined above, with a mixture offormaldehyde and a compound of formula (IX):R⁵—S—H  (IX)wherein R⁵ is as defined above with the exclusion of hydrogen. Thereaction may be performed in the presence or absence of a base such analkali metal carbonate, for example potassium carbonate, in a solventsuch as dioxan, tetrahydrofuran or N,N-dimethylformamide, at atemperature of from 0° to 100° C. (preferably 0° to 50° C.). Variousforms of formaldehyde may be used, for example paraformaldehyde, whenwater may also be present in the reaction mixture.

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁴, R⁶, A, W and n are as defined above, R⁵ is asdefined above with the exclusion of hydrogen, and m is 0, may beprepared by the reaction of a compound of formula (X):

wherein R¹, R², R³, R⁴, A, W and n are as defined above, with a compoundof formula (XI):R⁵-L³  (XI)wherein R⁵ is as defined above with the exclusion of hydrogen and L³ isa leaving group, generally a halogen for example chlorine or analkylsulphonyloxy group. The reaction is generally performed using analkali metal salt, for example the sodium salt, of the compound offormula (X), in an inert solvent such as tetrahydrofuran at atemperature from 0 to 60° C.

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁴, R⁵, R⁶, A, W and n are as defined above, and mis 0, may also be prepared by the reaction of a compound of formula(XII):

wherein R¹, R², R³, R⁴, A, W and n are as defined above and L⁴ is aleaving group, generally a halogen for example chlorine or analkylsulphonyloxy group, with a compound of formula (IX) as definedabove. The reaction is generally performed in the presence of a base,for example an alkali metal hydride such as sodium hydride, or an alkalimetal alkoxide such as potassium tert-butoxide, in an inert solvent suchas tetrahydrofuran at a temperature from 0 to 60° C., or an alkali metalcarbonate such as potassium carbonate, in an inert solvent such asacetone, at a temperature from 0° C. to the reflux temperature of thesolvent.

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁴, R⁶, W, m and n are as defined above, R⁵ is asdefined above with the exclusion of hydrogen, and A is (C₂-C₁₂)-alkyleneof which a two carbon chain links the R⁵S(O)_(m)— and —NR⁴— groups, mayalso be prepared by the reaction of a compound of formula (VI) abovewherein R¹, R², R³, R⁴, R⁶, W and n are as defined above, with acompound of formula (XIII):R⁵—S(O)_(m)-A¹  (XIII)wherein R⁵ and m are as defined above, and A¹ is a (C₂-C₁₂)-alkenylgroup in which the double bond is adjacent to the R⁵S(O)_(m) group. Thereaction is generally performed in an organic solvent, at a temperatureof from 0° to 200° C. (preferably 0° to 100° C.).

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁴, R⁶, A, W, and n are as defined above, R⁵ ishydrogen and m is 0, may be prepared by the reaction of thecorresponding compound of formula (XII) as defined above, with acompound of formula (XIV):R^(a)—C(═S)SH  (XIV)wherein R^(a) is (C₁-C₆)-alkyl, to give a compound of formula (XV);

wherein the various symbols are as defined above. The reaction isgenerally performed in the presence of a base such as an alkali metalhydride for example sodium hydride, an alkali metal alkoxide such assodium ethoxide, or triethylamine, in a solvent such as dioxan,tetrahydrofuran or N,N-dimethylformamide, at a temperature of from 0° to100° C. The compound of formula (XV) is then hydrolysed to give thecorresponding compound of formula (I) in which R⁵ is H. The hydrolysisis generally carried out using a base such as aqueous ammonia or analkali metal hydroxide such as sodium hydroxide, generally in thepresence of a co-solvent such as an alcohol for example ethanol, at atemperature of from 0° to 100° C. Alternatively the hydrolysis may beperformed in situ without isolation of (XV).

According to a further feature of the invention compounds of formula (I)wherein R¹, R², R³, R⁴, R⁵, R⁶, W and A are as defined above, and mand/or n is 1 or 2, may be prepared by oxidizing a correspondingcompound in which m and/or n is 0 or 1. The oxidation is generallyperformed using a peracid such as 3-chloroperbenzoic acid in a solventsuch as dichloromethane or 1,2-dichloroethane, at a temperature of from0° C. to the reflux temperature, of the solvent.

Collections of compounds of the formula (I) which can be synthesized bythe above mentioned process may also be prepared in a parallel manner,and this may be effected manually or in a semiautomated or fullyautomated manner. In this case, it is possible, for example, to automatethe procedure of the reaction, work-up or purification of the productsor of the intermediates. In total, this is to be understood as meaning aprocedure as is described, for example, by S. H. DeWitt in “AnnualReports in Combinatorial Chemistry and Molecular Diversity: Automated.Synthesis”, Volume 1, Verlag Escom 1997, pages 69 to 77.

A series of commercially available apparatuses as are offered by, forexample, Stem Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE,England or H+P Labortechnik GmbH, Bruckmannring 28, 85764Oberschleiβheim, Germany or Radleys, Shirehill, Saffron Walden, Essex,England, may be used for the parallel procedure of the reaction andwork-up. For the parallel purification of compounds of the formula (I),or of intermediates obtained during the preparation, use may be made,inter alia, of chromatography apparatuses, for example those by ISCO,Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.

The apparatuses mentioned lead to a modular procedure in which theindividual process steps are automated, but manual operations must beperformed between the process steps. This can be prevented by employingsemi-integrated or fully integrated automation systems where theautomation modules in question are operated by, for example, robots.Such automation systems can be obtained, for example, from ZymarkCorporation, Zymark Center, Hopkinton, Mass. 01748, USA.

In addition to what has been described here, compounds of the formula(I) may be prepared in part or fully by solid-phase-supported methods.For this purpose, individual intermediate steps or all intermediatesteps of the synthesis or of a synthesis adapted to suit the procedurein question are bound to a synthetic resin. Solid-phase-supportedsynthesis methods are described extensively in the specialistliterature, for example Barry A. Bunin in “The Combinatorial Index”,Academic Press, 1998.

The use of solid-phase-supported synthesis methods permits a series ofprotocols which are known from the literature and which, in turn, can beperformed manually or in an automated manner. For example, the “tea-bagmethod” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl.Acad. Sci, 1985, 82, 5131-5135), in which products by IRORI, 11149 NorthTorrey Pines Road, La Jolla, Calif. 92037, USA, are employed, may besemiautomated. The automation of solid-phase-supported parallelsyntheses is performed successfully, for example, by apparatuses byArgonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif.94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany.

The preparation of the processes described herein yields compounds ofthe formula (I) in the form of substance collections which are termedlibraries. The present invention also relates to libraries whichcomprise at least two compounds of the formula (I).

Intermediates of formula (II) wherein L is chlorine, bromine or iodinemay be prepared according to known procedures, for example as describedin EP 0295117, by the diazotization of the corresponding amine offormula (VIII), generally using an alkyl nitrite such as t-butylnitrite, in the presence of a suitable halogenating agent, preferablybromoform, iodine or anhydrous cupric chloride, optionally in thepresence of a solvent such as acetonitrile or chloroform, at atemperature of from 0° to 100° C.

Some of the compounds of formula (IV) and (X) are included in thedefinition of formula (I) and may be prepared by the above-mentionedmethods, whilst the other compounds of formula (IV) and (X) are known ormay be prepared by known methods.

Compounds of formula (XV) are novel and as such form a further featureof the invention.

Compounds of formula (II), (III), (V), (VI), (VII), (VIII), (IX), (XI),(XII), (XIII) and (XIV) are known or may be prepared by known methods.

CHEMICAL EXAMPLES

The following non-limiting Examples illustrate the preparation of thecompounds of formula (I).

NMR spectra were run in deuterochloroform unless stated otherwise. Inthe Examples which follow, quantities (also percentages) areweight-based, unless stated otherwise.

Example 1

To a solution of5-bromo-1(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfonylpyrazole(5.0 g, 9.7 mmol) in 1,4-dioxane (20 ml) and N,N-dimethylformamide (20ml) was added 3-ethylthiopropylamine (2.306 g, 19.3 mmol) and potassiumcarbonate (2.7 g, 19.3 mmol). The resulting mixture was stirred at 20°C. for 2.75 hours, left to stand overnight, then poured into a mixtureof water and dichloromethane. The organic phase was washed with water,dried (sodium sulfate), evaporated and chromatographed on silica gel,eluting with heptane-ethyl acetate (4:1) to give1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(3-ethylthiopropylamino)-4-trifluoromethylsulfonylpyrazoleas a yellow solid (Compound number 1-14, 4.79 g, 86% yield), mp 80° C.

Example 2

To a solution of1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(3-ethylthiopropylamino)-4-trifluoromethylsulfonylpyrazole(2.0 g, 3.6 mmol) in tetrahydrofuran at 20° C. under nitrogen, was addedsodium hydride (0.461 g, 60% in oil, 11.5 mmol), and stirred for 0.5hour. Iodomethane (2.065 g, 14.4 mmol) was added and the mixture stirredfor 4.5 hours at 20° C., then allowed to stand for 2.5 days. The mixturewas added to ethyl acetate and saturated ammonium chloride solution. Theorganic layer was washed with water and brine, dried (sodium sulfate),evaporated and chromatographed on silica gel eluting with heptane-ethylacetate (3:1) to give1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-(3-ethylthiopropyl)-N-methylamino]-4-trifluoromethylsulfonylpyrazoleas a light brown solid (Compound number 2-14, 1.3 g, 57% yield), mp 89°C.

Example 3

m-Chloroperbenzoic acid (0.091 g, 77%, 0.4 mmol) was added to a solutionof1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-(3-ethylthiopropyl)-N-methylamino]-4-trifluoromethylsulfonylpyrazole(0.23 g, 0.4 mmol) in 1,2-dichloroethane at 0-5° C. The mixture wasstirred at 0-5° C. for 0.5 hour, then poured into saturated sodiumbicarbonate and ethyl acetate. The organic layer was washed with brine,dried (sodium sulfate), evaporated and chromatographed on silica geleluting with heptane-ethyl acetate (1/1 to 3/7) to give1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-(ethylsulfinylpropyl)-N-methylamino]-4-trifluoromethylsulfonylpyrazoleas a light brown oil (Compound number 2-15, 0.186 g, 71%),19F: −63.8,−78.7.

Example 4

Sodium hydride (0.172 g, 4.3 mmol) was added to a solution of1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-N-methylamino-4-trifluoromethylthiopyrazole(1.5 g, 3.4 mmol) in tetrahydrofuran cooled by an ice water bath. Theice bath was removed and the mixture stirred at 20° C. for 0.75 hour andchloromethylmethylsulfide (0.456 g, 4.5 mmol) added. The mixture wasstirred at 20° C. for 6.5 hours and heated under reflux for 2 hours,then cooled and added to saturated ammonium chloride and ethyl acetate.The organic layer was washed with water and brine, dried (sodiumsulfate), evaporated and chromatographed on silica gel eluting withheptane-ethyl acetate (9:1) to give1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-methyl-N-(methylthiomethyl)amino]-4-trifluoromethylthiopyrazoleas a light yellow oil (Compound number 2-25, 0.59 g, 35% yield), 19F:−43.9, −63.7.

Example 5

Sodium hydride (0.032 g, 60%, 0.8 mmol) was added to a solution of1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(3-ethylthiopropylamino)-4-trifluoromethylsulfonylpyrazole(0.3 g, 0.54 mmol) in tetrahydrofuran 20° C. under nitrogen. The mixturewas stirred at 20° C. for one hour then ethyl chloroformate (0.121 g,1.1 mmol) was added. The mixture was stirred at 20° C. for 5 hours, thenpoured into saturated ammonium chloride and ethyl acetate. The organiclayer was washed with water and brine, dried (sodium sulfate),evaporated to provide and purified by chromatography on silica geleluting with heptane-ethyl acetate (4:1) to give1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-[N-ethoxycarbonyl-N-(3-ethylthiopropyl)amino]-4-trifluoromethylsulfonylpyrazoleas an oil (Compound number 3-14, 0.278 g, 81% yield), 19F: −63.9; −77.9.

Example 6

To a solution of3-cyano-5-methylamino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole(0.5 g, 1.1 mmol) in tetrahydrofuran was added sodium hydride (60%, 0.06g, 1.4 mmol), then 2-chloroethyl-phenylsulfone (0.27 g, 1.3 mmol). Themixture was heated at reflux for 10 hours. After extractive workup andcolumn chromatography with heptane-ethyl acetate (1:1) there wasobtained1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-N-(2-phenylsulfonylethyl)-N-methylamino-4-trifluoromethylsulfinylpyrazole(Compound number 2-38, 0.26 g), 19F: −64.1; −73.0.

Example 7

To a solution of1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-(2-phenylthioethyl)amino-4-trifluoromethylthiopyrazole(0.15 g, 0.27 mmol) in tetrahydrofuran was added ethyl chloroformate (58mg, 0.54 mmol) and diisopropylethylamine (70 mg, 0.54 mmol) and4-dimethylaminopyridine (10 mg). The mixture was heated at reflux for 1hour. After extractive workup and column chromatography withheptane-ethyl acetate (1:1) there was obtained1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-N-(2-phenylthioethyl)-N-ethoxycarbonylamino-4-trifluoromethylthiopyrazole(Compound number 3-109, 0.07 g), 19F: −63.7; −70.8.

The following Reference Example illustrates the preparation ofintermediates used in the synthesis of the above Examples.

Reference Example 1

t-Butylnitrite (84 ml, 0.662 mol) was added to a suspension of5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfonylpyrazole(100 g, 0.221 mol) in bromoform (320 ml). The resulting mixture washeated to 60-70° C. for 3 hours. Another portion of t-butylnitrite (84ml, 0.662 mol) was added and the mixture stirred at 60-70° C. for afurther 2.5 hours. It was then cooled, washed with hexane,hexane-toluene, and then filtered. The solid was washed with pentane andvacuum dried to give5-bromo-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfonylpyrazoleas a yellow solid (96.69 g, 79% yield), mp 142° C.

The following preferred compounds shown in Tables 1 to 12 also form partof the present invention, and were or may be prepared in accordancewith, or analogously to, the above-mentioned Examples 1 to 7 or theabove-described general methods. In the Tables, Et means ethyl, i-Prmeans isopropyl, n-Bu means n-butyl, t-Bu means tert-butyl, Ph meansphenyl and 2-THF means 2-tetrahydrofuryl. Where subscripts are omittedafter atoms it will be understood that they are intended, for exampleCH₃ means CH₃.

19F-NMR spectra shift values are given in ppm.

Compound numbers are given for reference purposes only.

TABLE I Compounds of formula (I) in which the substituents have thefollowing meanings: R¹ = CN, R⁶ is CF₃, R⁴ is hydrogen, W = C—Cl, R² =Cl, R³ = CF₃. Compound m.p. (° C.), or Number A S(O)_(m) R5 n NMR(ppm)1-1 CH2CH2 S CH3 0 1-2 CH2CH2 S CH3 2 105-106 1-3 CH2CH2 SO CH3 2 1-4CH2CH2 SO2 CH3 2 161-164 1-5 CH2CH2 SO CH3 1 190-191 1-6 CH2CH2CH2 S CH30 1-7 CH2CH2CH2 S CH3 1 1-8 CH2CH2CH2 S CH3 2 121-122 1-9 CH2CH2CH2 SOCH3 2 140-141 1-10 CH2CH2CH2 SO2 CH3 2 183-184 1-11 CH2CH2CH2 SO CH3 01-12 CH2CH2CH2 S CH2CH3 0 1-13 CH2CH2CH2 S CH2CH3 1 1-14 CH2CH2CH2 SCH2CH3 2 80 1-15 CH2CH2CH2 SO CH2CH3 2 118 1-16 CH2CH2CH2 SO2 CH2CH3 0oil 1-17 CH2CH2 S CH2Ph 2 137 1-18 CH2CH2 S CH2CH3 0 1-19 CH2CH2 SCH2CH3 2 86 1-20 CH2CH2 SO2 Ph 0 1-21 CH2CH2 S cyclohexyl 0 1-22 CH2 Si-Pr 0 168.5 1-23 CH2 S cyclopentyl 0 1-24 CH2 S CH2CF3 2 1-25 CH2 S CH30 1-26 CH2 S CH3 1 1-27 CH2 S CH3 2 1-28 CH2 SO CH3 2 1-29 CH2CH2CH2CH2S CH3 2 1-30 CH2CH2CH2CH2 SO CH3 0 1-31 CH2CH2CH2CH2 S CH2CH3 1 1-32CH2CH2CH2 S t-Bu 2 1-33 CH2CH2CH2 SO t-Bu 2 1-34 CH2CH2 SO2 Et 2 1321-35 CH2CH2 SO CH2CH3 2 172 1-36 3-tetrahydrothienyl 2 130-135 1-373-tetrahydrothienyl sulfoxide 2 19F: −63.8, −79.8 1-383-tetrahydrothienyl sulfone 2 19F: −63.2, −79.9 1-39 CH2CH2 SO CH2Ph 2162 1-40 CH2CH2 SO2 CH2Ph 2 156 1-41 CH2CH2 S CH3 1 165 1-42 CH2CH2 S Ph1 19F: −64.2; −74.0 1-43 CH2CH2 S Ph 0 19F: −45.4; −63.6 1-44 CH2CH2 SO2Ph 1 19F: −64.2; −74.0 1-45 CH2CH2 SO CH3 0 1-46 CH2CH2 SO2 CH3 0 1-47CH2CH2 SO2 CH3 1 1-48 CH2CH2 SO2 Ph 2 1-49 CH2CH2 S Ph 2 1-50 CH2CH2 SOPh 0 1-51 CH2CH2 SO Ph 1 1-52 CH2CH2 SO Ph 2 1-53 CH2CH2 S CH2Ph 0 1-54CH2CH2 S CH2Ph 1 1-55 CH2CH2 SO CH2Ph 0 1-56 CH2CH2 SO CH2Ph 1 1-57CH2CH2 S cyclopropyl 0 1-58 CH2CH2 S cyclobutyl 0 1-59 CH2CH2 Scyclopentyl 0 1-60 CH2CH2 S allyl 0 1-61 CH2CH2 SO2 NMe2 0 1-62 CH2CH2SO2 NEt2 0 1-63 CH2CH2 SO2 NMe2 1 1-64 CH2CH2 SO2 NEt2 1 1-65 CH2CH2CH2SO2 NMe2 0 1-66 CH2CH2CH2 SO2 NMe2 1 1-67 CH2CH2CH2 SO2 NMe2 2 1-68CH2CH2CH2 SO2 NEt2 0 1-69 CH2CH2CH2 SO2 NEt2 1 1-70 CH2CH2CH2 SO2 NEt2 21-71 CH2CH2CH2 SO2 N-iPr2 0 1-72 CH2CH2CH2 SO2 N-iPr2 1 1-73 CH2CH2CH2SO2 N-iPr2 2 1-74 CH2CH2CH2 SO2 N-nBu2 0 1-75 CH2CH2CH2 SO2 N-nBu2 11-76 CH2CH2CH2 SO2 N-nBu2 2 1-77 CH2CH2CH2 SO2 N-pyrrolidinyl 0 1-78CH2CH2CH2 SO2 N-pyrrolidinyl 1 1-79 CH2CH2CH2 SO2 N-pyrrolidinyl 2 1-80CH2CH2CH2 SO2 N-piperidinyl 0 1-81 CH2CH2CH2 SO CH3 1 1-82 CH2CH2CH2 SO2CH3 0 1-83 CH2CH2CH2 SO2 CH3 1 1-84 CH2CH2CH2 S Ph 0 1-85 CH2CH2CH2 SOPh 0 1-86 CH2CH2CH2 SO2 Ph 0 1-87 CH2CH2CH2 S Ph 1 1-88 CH2CH2CH2 SO Ph1 1-89 CH2CH2CH2 SO2 Ph 1 1-90 CH2CH2CH2 S Ph 2 1-91 CH2CH2CH2 SO Ph 21-92 CH2CH2CH2 SO2 Ph 2 1-93 CH(CH3)CH2 S CH3 0 1-94 CH(CH3)CH2 S CH3 11-95 CH(CH3)CH2 S CH3 2 1-96 CH(CH3)CH2 SO CH3 0 1-97 CH(CH3)CH2 SO CH31 1-98 CH(CH3)CH2 SO CH3 2 1-99 CH(CH3)CH2 SO2 CH3 0 1-100 CH(CH3)CH2SO2 CH3 1 1-101 CH(CH3)CH2 SO2 CH3 2 1-102 CH2CH(CH3) S CH3 0 1-103CH2CH(CH3) S CH3 1 1-104 CH2CH(CH3) S CH3 2 1-105 CH2CH(CH3) SO CH3 01-106 CH2CH(CH3) SO CH3 1 1-107 CH2CH(CH3) SO CH3 2 1-108 CH2CH(CH3) SO2CH3 0 1-109 CH2CH(CH3) SO2 CH3 1 1-110 CH2CH(CH3) SO2 CH3 2 1-111CH2CH2CH2 S Ph 0 1-112 CH2CH2CH2 S Ph 1 1-113 CH2CH2CH2 S Ph 2 1-114CH2CH2CH2 SO Ph 1 1-115 CH2CH2CH2 SO Ph 2 1-116 CH2CH2CH2 SO Ph 2 1-117CH2CH2CH2 SO2 Ph 0 1-118 CH2CH2CH2 SO2 Ph 1 1-119 CH2CH2CH2 SO2 Ph 21-120 CH2CH2CH2 S CH2Ph 0 1-121 CH2CH2CH2 S CH2Ph 1 1-122 CH2CH2CH2 SCH2Ph 2 1-123 CH2CH2CH2 SO CH2Ph 1 1-124 CH2CH2CH2 SO CH2Ph 2 1-125CH2CH2CH2 SO CH2Ph 2 1-126 CH2CH2CH2 SO2 CH2Ph 0 1-127 CH2CH2CH2 SO2CH2Ph 1 1-128 CH2CH2CH2 SO2 CH2Ph 2

TABLE II R¹ = CN, R⁶ = CF₃, R⁴ = CH₃, W = C—Cl, R² = Cl, R³ = CF₃Compound m.p. (° C.); Number A S(O)_(m) R5 n NMR(ppm) 2-1 CH2CH2 S CH3 02-2 CH2CH2 S CH3 2 81 2-3 CH2CH2 SO CH3 2 142 2-4 CH2CH2 SO2 CH3 2 1482-5 CH2CH2 SO CH3 1 55.5 2-6 CH2CH2CH2 S CH3 0 2-7 CH2CH2CH2 S CH3 1 2-8CH2CH2CH2 S CH3 2 94-95 2-9 CH2CH2CH2 SO CH3 2 106-107 2-10 CH2CH2CH2SO2 CH3 2 160-161 2-11 CH2CH2CH2 SO CH3 0 2-12 CH2CH2CH2 S CH2CH3 0 2-13CH2CH2CH2 S CH2CH3 1 2-14 CH2CH2CH2 S CH2CH3 2 89 2-15 CH2CH2CH2 SOCH2CH3 2 19F: −63.8, −78.7 2-16 CH2CH2CH2 SO2 CH2CH3 0 2-17 CH2CH2 SCH2Ph 2 103 2-18 CH2CH2 S CH2CH3 0 2-19 CH2CH2 S CH2CH3 2 103 2-20CH2CH2 SO2 Ph 0 2-21 CH2CH2 S cyclohexyl 0 2-22 CH2 S i-Pr 0 2-23 CH2 Scyclopentyl 0 2-24 CH2 S CH2CF3 2 2-25 CH2 S CH3 0 19F: −43.9, −63.72-26 CH2 S CH3 1 19F: −63.7, −71.9 2-27 CH2 S CH3 2 19F: −63.8, −78.62-28 CH2 SO CH3 2 2-29 CH2CH2CH2CH2 S CH3 2 2-30 CH2CH2CH2CH2 SO CH3 02-31 CH2CH2CH2CH2 S CH2CH3 1 2-32 CH2CH2CH2 S t-Bu 2 2-33 CH2CH2CH2 SOt-Bu 2 2-34 CH2CH2 SO CH2CH3 2 19F: −63.8, −78.6 2-35 CH2CH2 SO2 CH2CH32 19F: −63.8, −78.7 2-36 CH2CH2CH2 SO2 CH2CH3 2 19F: −63.8, −78.6 2-37CH2CH2 SO2 Ph 0 157 2-38 CH2CH2 SO2 Ph 1 19F: −64.1; −73.0 2-39 CH2CH2SO2 Ph 2 2-40 CH2CH2 S Ph 0 2-41 CH2CH2 S Ph 1 2-42 CH2CH2 S Ph 2 2-43CH2CH2 SO Ph 0 2-44 CH2CH2 SO Ph 1 2-45 CH2CH2 SO Ph 2 2-46 CH2CH2 SO2CH2Ph 0 2-47 CH2CH2 SO2 CH2Ph 1 2-48 CH2CH2 SO2 CH2Ph 2 2-49 CH2CH2 SOCH2Ph 0 2-50 CH2CH2 SO CH2Ph 1 2-51 CH2CH2 SO CH2Ph 2 2-52 CH2CH2 SCH2Ph 0 2-53 CH2CH2 S CH2Ph 1 2-54 CH2CH2 S CH3 1 2-55 CH2CH2 SO CH3 088 2-56 CH2CH2 SO2 CH3 0 118-120 2-57 CH2CH2 SO2 CH3 1 130-132 2-58CH2CH2CH2 SO CH3 1 2-59 CH2CH2CH2 SO2 CH3 0 2-60 CH2CH2CH2 SO2 CH3 12-61 CH(CH3)CH2 S CH3 0 2-62 CH(CH3)CH2 S CH3 1 2-63 CH(CH3)CH2 S CH3 22-64 CH(CH3)CH2 SO CH3 0 2-65 CH(CH3)CH2 SO CH3 1 2-66 CH(CH3)CH2 SO CH32 2-67 CH(CH3)CH2 SO2 CH3 0 2-68 CH(CH3)CH2 SO2 CH3 1 2-69 CH(CH3)CH2SO2 CH3 2 2-70 CH2CH(CH3) S CH3 0 2-71 CH2CH(CH3) S CH3 1 2-72CH2CH(CH3) S CH3 2 2-73 CH2CH(CH3) SO CH3 0 2-74 CH2CH(CH3) SO CH3 12-75 CH2CH(CH3) SO CH3 2 2-76 CH2CH(CH3) SO2 CH3 0 2-77 CH2CH(CH3) SO2CH3 1 2-78 CH2CH(CH3) SO2 CH3 2 2-79 CH2CH2 SO2 NMe2 0 2-80 CH2CH2 SO2NEt2 0 2-81 CH2CH2 SO2 NMe2 1 2-82 CH2CH2 SO2 NEt2 1 2-83 CH2CH2CH2 SO2NMe2 0 2-84 CH2CH2CH2 SO2 NMe2 1 2-85 CH2CH2CH2 SO2 NMe2 2 2-86CH2CH2CH2 SO2 NEt2 0 19F: −44.40, −63.71 2-87 CH2CH2CH2 SO2 NEt2 1 2-88CH2CH2CH2 SO2 NEt2 2 2-89 CH2CH2CH2 SO2 N-iPr2 0 2-90 CH2CH2CH2 SO2N-iPr2 1 2-91 CH2CH2CH2 SO2 N-iPr2 2 2-92 CH2CH2CH2 SO2 N-nBu2 0 2-93CH2CH2CH2 SO2 N-nBu2 1 2-94 CH2CH2CH2 SO2 N-nBu2 2 2-95 CH2CH2CH2 SO2N-pyrrolidinyl 0 2-96 CH2CH2CH2 SO2 N-pyrrolidinyl 1 2-97 CH2CH2CH2 SO2N-pyrrolidinyl 2 2-98 CH2CH2CH2 SO2 N-piperidinyl 0 2-99 CH2CH2CH2 SO2N-piperidinyl 1 2-100 CH2CH2CH2 SO2 N-piperidinyl 2 2-101 CH2CH2CH2 S Ph0 2-102 CH2CH2CH2 S Ph 1 2-103 CH2CH2CH2 S Ph 2 2-104 CH2CH2CH2 SO Ph 12-105 CH2CH2CH2 SO Ph 2 2-106 CH2CH2CH2 SO Ph 2 2-107 CH2CH2CH2 SO2 Ph 02-108 CH2CH2CH2 SO2 Ph 1 2-109 CH2CH2CH2 SO2 Ph 2 2-110 CH2CH2CH2 SCH2Ph 0 2-111 CH2CH2CH2 S CH2Ph 1 2-112 CH2CH2CH2 S CH2Ph 2 2-113CH2CH2CH2 SO CH2Ph 1 2-114 CH2CH2CH2 SO CH2Ph 2 2-115 CH2CH2CH2 SO CH2Ph2 2-116 CH2CH2CH2 SO2 CH2Ph 0 2-117 CH2CH2CH2 SO2 CH2Ph 1 2-118CH2CH2CH2 SO2 CH2Ph 2

TABLE III R¹ = CN, R⁶ = CF₃, R⁴ = CO₂CH₂CH₃, W = C—Cl, R² = Cl, R³ = CF₃Cpd Number A S(O)_(m) R5 n m.p. (° C.) NMR(ppm) 3-1 CH2CH2 S CH3 0 19F:−41.8; −63.8 3-2 CH2CH2 S CH3 2 19F: −63.8; −77.7 3-3 CH2CH2 SO CH3 219F: −63.8, −63.9, −77.4, −77.6 3-4 CH2CH2 SO2 CH3 2 152 3-5 CH2CH2 SOCH2CF2H 1 3-6 CH2CH2CH2 S CH3 0 3-7 CH2CH2CH2 S CH3 1 3-8 CH2CH2CH2 SCH3 2  82 3-9 CH2CH2CH2 SO CH3 2 19F: −63.7; −63.8; −77.5 3-10 CH2CH2CH2SO2 CH3 2 124-127 3-11 CH2CH2CH2 SO CH3 0 3-12 CH2CH2CH2 S CH2CH3 0 3-13CH2CH2CH2 S CH2CH3 1 3-14 CH2CH2CH2 S CH2CH3 2 19F: −63.9; −77.9 3-15CH2CH2CH2 SO CH2CH3 2 3-16 CH2CH2CH2 SO2 CH2CH3 0 3-17 CH2CH2 S CH2Ph 23-18 CH2CH2 S CH2CH3 0 3-19 CH2CH2 S CH2CH3 2 19F: −63.8; −77.7 3-20CH2CH2 SO2 Ph 0 3-21 CH2CH2 S cyclohexyl 0 3-22 CH2 S i-Pr 0 3-23 CH2 Scyclopentyl 0 3-24 CH2 S CH2CF3 2 3-25 CH2 S CH3 0 3-26 CH2 S CH3 1 3-27CH2 S CH3 2 3-28 CH2 SO CH3 2 3-29 CH2CH2CH2CH2 S CH3 2 3-30CH2CH2CH2CH2 SO CH3 0 3-31 CHCH2CH2CH2 S CH2CH3 1 3-32 CH2CH2CH2 S t-Bu2 3-33 CH2CH2CH2 SO t-Bu 2 3-34 CH2CH2 S CH3 1 134-136 3-35 CH2CH2 SOCH3 0 19F: −41.9; −63.8 3-36 CH2CH2 SO CH3 1 152-154 3-37 CH2CH2 SO2 CH30 132-135 3-38 CH2CH2 SO2 CH3 1 19F: −63.8; −70.8 3-39 CH2CH2CH2 SO CH31 3-40 CH2CH2CH2 SO2 CH3 0 3-41 CH2CH2CH2 SO2 CH3 1 3-42 CH(CH3)CH2 SCH3 0 3-43 CH(CH3)CH2 S CH3 1 3-44 CH(CH3)CH2 S CH3 2 3-45 CH(CH3)CH2 SOCH3 0 3-46 CH(CH3)CH2 SO CH3 1 3-47 CH(CH3)CH2 SO CH3 2 3-48 CH(CH3)CH2SO2 CH3 0 3-49 CH(CH3)CH2 SO2 CH3 1 3-50 CH(CH3)CH2 SO2 CH3 2 3-51CH2CH(CH3) S CH3 0 3-52 CH2CH(CH3) S CH3 1 3-53 CH2CH(CH3) S CH3 2 3-54CH2CH(CH3) SO CH3 0 3-55 CH2CH(CH3) SO CH3 1 3-56 CH2CH(CH3) SO CH3 23-57 CH2CH(CH3) SO2 CH3 0 3-58 CH2CH(CH3) SO2 CH3 1 3-59 CH2CH(CH3) SO2CH3 2 3-60 CH2CH2 SO2 NMe2 0 3-61 CH2CH2 SO2 NEt2 0 3-62 CH2CH2 SO2 NMe21 3-63 CH2CH2 SO2 NEt2 1 3-64 CH2CH2CH2 SO2 NMe2 0 3-65 CH2CH2CH2 SO2NMe2 1 3-66 CH2CH2CH2 SO2 NMe2 2 3-67 CH2CH2CH2 SO2 NEt2 0 3-68CH2CH2CH2 SO2 NEt2 1 3-69 CH2CH2CH2 SO2 NEt2 2 3-70 CH2CH2CH2 SO2 N-iPr20 3-71 CH2CH2CH2 SO2 N-iPr2 1 3-72 CH2CH2CH2 SO2 N-iPr2 2 3-73 CH2CH2CH2SO2 N-nBu2 0 3-74 CH2CH2CH2 SO2 N-nBu2 1 3-75 CH2CH2CH2 SO2 N-nBu2 23-76 CH2CH2CH2 SO2 N-pyrrolidinyl 0 3-77 CH2CH2CH2 SO2 N-pyrrolidinyl 13-78 CH2CH2CH2 SO2 N-pyrrolidinyl 2 3-79 CH2CH2CH2 SO2 N-piperidinyl 03-80 CH2CH2CH2 SO2 N-piperidinyl 1 3-81 CH2CH2CH2 SO2 N-piperidinyl 23-82 CH2CH2CH2 S Ph 0 3-83 CH2CH2CH2 S Ph 1 3-84 CH2CH2CH2 S Ph 2 3-85CH2CH2CH2 SO Ph 1 3-86 CH2CH2CH2 SO Ph 2 3-87 CH2CH2CH2 SO Ph 2 3-88CH2CH2CH2 SO2 Ph 0 3-89 CH2CH2CH2 SO2 Ph 1 3-90 CH2CH2CH2 SO2 Ph 2 3-91CH2CH2CH2 S CH2Ph 0 3-92 CH2CH2CH2 S CH2Ph 1 3-93 CH2CH2CH2 S CH2Ph 23-94 CH2CH2CH2 SO CH2Ph 1 3-95 CH2CH2CH2 SO CH2Ph 2 3-96 CH2CH2CH2 SOCH2Ph 2 3-97 CH2CH2CH2 SO2 CH2Ph 0 3-98 CH2CH2CH2 SO2 CH2Ph 1 3-99CH2CH2CH2 SO2 CH2Ph 2 3-100 CH2CH2 SO2 Ph 1 3-101 CH2CH2 SO2 Ph 2 3-102CH2CH2 S Ph 0 19F: −42.4; −64.2 3-103 CH2CH2 S Ph 1 3-104 CH2CH2 S Ph 23-105 CH2CH2 SO Ph 0 3-106 CH2CH2 SO Ph 1 3-107 CH2CH2 SO Ph 2 3-108CH2CH2 SO2 CH2Ph 0 3-109 CH2CH2 SO2 Ph 1 19F: −63.7; −70.8 3-110 CH2CH2SO2 CH2Ph 2 3-111 CH2CH2 SO CH2Ph 0 3-112 CH2CH2 SO CH2Ph 1 3-113 CH2CH2SO CH2Ph 2 3-114 CH2CH2 S CH2Ph 0 3-115 CH2CH2 S CH2Ph 1

TABLE IV R¹ = CN, R⁶ = CF₃, R⁴ = CH₂OCH₂CH₃, W = C—Cl, R² = Cl, R³ = CF₃Cpd m.p. (° C.) or Number A S(O)_(m) R5 n NMR(ppm) 4-1 CH2CH2 S CH3 04-2 CH2CH2 S CH3 2 19F: −63.7; −78.6 4-3 CH2CH2 SO CH3 2 4-4 CH2CH2 SO2CH3 2 4-5 CH2CH2 SO CH3 1 4-6 CH2CH2CH2 S CH3 0 4-7 CH2CH2CH2 S CH3 14-8 CH2CH2CH2 S CH3 2 4-9 CH2CH2CH2 SO CH3 2 19F: −63.7, −78.6 4-10CH2CH2CH2 SO2 CH3 2 4-11 CH2CH2CH2 SO CH3 0 4-12 CH2CH2CH2 S CH2CH3 04-13 CH2CH2CH2 S CH2CH3 1 4-14 CH2CH2CH2 S CH2CH3 2 4-15 CH2CH2CH2 SOCH2CH3 2 4-16 CH2CH2CH2 SO2 CH2CH3 0 4-17 CH2CH2 S CH2Ph 2 4-18 CH2CH2 SCH2CH3 0 4-19 CH2CH2 S CH2CH3 2 4-20 CH2CH2 SO2 Ph 0 4-21 CH2CH2 Scyclohexyl 0 4-22 CH2 S i-Pr 0 4-23 CH2 S cyclopentyl 0 4-24 CH2 SCH2CF3 2 4-25 CH2 S CH3 0 4-26 CH2 S CH3 1 4-27 CH2 S CH3 2 4-28 CH2 SOCH3 2 4-29 CH2CH2CH2CH2 S CH3 2 4-30 CH2CH2CH2CH2 SO CH3 0 4-31CHCH2CH2CH2 S CH2CH3 1 4-32 CH2CH2CH2 S t-Bu 2 4-33 CH2CH2CH2 SO t-Bu 2

TABLE V R¹ = CN, R⁶ = CF₃, R⁴ = H, W = C—Cl, R² = Cl, R³ = OCF₃ CpdNumber A S(O)_(m) R5 n m.p. (° C.) 5-1 CH2CH2 S CH3 0 5-2 CH2CH2 S CH3 293 5-3 CH2CH2 SO CH3 2 5-4 CH2CH2 SO2 CH3 2 5-5 CH2CH2 SO CH3 1 5-6CH2CH2CH2 S CH3 0 5-7 CH2CH2CH2 S CH3 1 5-8 CH2CH2CH2 S CH3 2 80 5-9CH2CH2CH2 SO CH3 2 5-10 CH2CH2CH2 SO2 CH3 2 5-11 CH2CH2CH2 SO CH3 0 5-12CH2CH2CH2 S CH2CH3 0 5-13 CH2CH2CH2 S CH2CH3 1 5-14 CH2CH2CH2 S CH2CH3 25-15 CH2CH2CH2 SO CH2CH3 2 5-16 CH2CH2CH2 SO2 CH2CH3 0 5-17 CH2CH2 SCH2Ph 2 5-18 CH2CH2 S CH2CH3 0 5-19 CH2CH2 S CH2CH3 2 5-20 CH2CH2 SO2 Ph0 5-21 CH2CH2 S cyclohexyl 0 5-22 CH2 S i-Pr 0 5-23 CH2 S cyclopentyl 05-24 CH2 S CH2CF3 2 5-25 CH2 S CH3 0 5-26 CH2 S CH3 1 5-27 CH2 S CH3 25-28 CH2 SO CH3 2 5-29 CH2CH2CH2CH2 S CH3 2 5-30 CH2CH2CH2CH2 SO CH3 05-31 CHCH2CH2CH2 S CH2CH3 1 5-32 CH2CH2CH2 S t-Bu 2 5-33 CH2CH2CH2 SOt-Bu 2

TABLE VI R¹ = CN, R⁶ = CF₃, R⁴ = CH₃, W = C—Cl, R² = Cl, R³ = OCF₃ CpdNumber A S(O)_(m) R5 n m.p. (° C.) 6-1 CH2CH2 S CH3 0 6-2 CH2CH2 S CH3 298 6-3 CH2CH2 SO CH3 2 6-4 CH2CH2 SO2 CH3 2 6-5 CH2CH2 SO CH3 1 6-6CH2CH2CH2 S CH3 0 6-7 CH2CH2CH2 S CH3 1 6-8 CH2CH2CH2 S CH3 2 79 6-9CH2CH2CH2 SO CH3 2 6-10 CH2CH2CH2 SO2 CH3 2 6-11 CH2CH2CH2 SO CH3 0 6-12CH2CH2CH2 S CH2CH3 0 6-13 CH2CH2CH2 S CH2CH3 1 6-14 CH2CH2CH2 S CH2CH3 26-15 CH2CH2CH2 SO CH2CH3 2 6-16 CH2CH2CH2 SO2 CH2CH3 0 6-17 CH2CH2 SCH2Ph 2 6-18 CH2CH2 S CH2CH3 0 6-19 CH2CH2 S CH2CH3 2 6-20 CH2CH2 SO2 Ph0 6-21 CH2CH2 S cyclohexyl 0 6-22 CH2 S i-Pr 0 6-23 CH2 S cyclopentyl 06-24 CH2 S CH2CF3 2 6-25 CH2 S CH3 0 6-26 CH2 S CH3 1 6-27 CH2 S CH3 26-28 CH2 SO CH3 2 6-29 CH2CH2CH2CH2 S CH3 2 6-30 CH2CH2CH2CH2 SO CH3 06-31 CHCH2CH2CH2 S CH2CH3 1 6-32 CH2CH2CH2 S t-Bu 2 6-33 CH2CH2CH2 SOt-Bu 2

TABLE VII R⁵ = Me, R² = Cl, W = C—Cl; R³ = CF₃ Cpd No. R¹ R⁶ R⁴ n AS(O)_(m) m.p. (° C.) 7-1 CN CClF2 H 2 CH2CH2 S 7-2 CN CCl2F H 1CH2CH2CH2 S 7-3 CN CHF2 CH3 2 CH2CH2CH2 S 7-4 CN CBrF2 CH3 0 CH2 S 7-5CF3 CClF2 H 2 CH2CH2 S 7-6 CF3 CCl2F H 1 CH2CH2CH2 S 7-7 CF3 CHF2 CH3 2CH2CH2CH2 S 7-8 CF3 CBrF2 CH3 0 CH2 S 7-9 CN CH3 CH3 1 CH2CH2 S 7-10 CNCH3 H 1 CH2CH2 S

TABLE VIII R¹ = CN; R² = Cl; W = C—Cl; R³ = CF₃; R⁵ = CH₃: Cpd m.p. (°C.) No. R⁴ A S(O)_(m) n R⁶ NMR 8-1 CO2Me CH2CH2 S 2 CF3 135 8-2 CH2CH3CH2CH2 S 2 CF3 98 8-3 CH2SCH3 CH2CH2 S 2 CF3 19F: −63.6, −78.1 8-4CO2CH3 CH2CH2CH2 SO 2 CF3 19F: −63.7, −77.4 8-5 CH2CH2SCH3 CH2CH2CH2 S 2CF3 19F: −67.7, −78.3 8-6 CH2SCH3 CH2CH2CH2 S 2 CF3 19F: −64.1, −78.78-7 CH2cyclopropyl CH2CH2 S 2 CF3 Solid 8-8 CH2cyclopropyl CH2CH2CH2CH2S 2 CF3 19F: −63.9, −78.2 8-9 CH2CH3 CH2CH2CH2 S 2 CF3 19F: −64.1, −78.98-10 cyclopropyl CH2 S 2 CF3 134 8-11 cyclopropyl CH2CH2 S 2 CF3 1518-12 CH2CH3 CH2CH2 SO 2 CF3 19F: −63.7, −78.3 8-13 CH2CH═CH2 CH2CH2 SO 2CF3 147 8-14 CH2SCH3 CH2CH2 SO 2 CF3 19F: −64.1, −78.7 8-15 CH2CH3CH2CH2CH2 SO 2 CF3 19F: −63.7, −78.3 8-16 CH2CH═CH2 CH2CH2CH2 SO 2 CF3124 8-17 CH2SCH3 CH2CH2CH2 SO 2 CF3 19F: −64.1, −78.7 8-18CH2cyclopropyl CH2 S 0 CF3 19F: −43.3, −63.9 8-19 CH2cyclopropyl CH2CH2S 1 CF3 19F: −63.7, −71.9 8-20 CH2cyclopropyl CH2 S 2 CF3 19F: −64.7,−78.6 8-21 CH2CH═CH2 CH2CH2 S 1 CF3 101 8-22 CH2CH3 CH2CH2 S 1 CF3 19F:−63.7, −72.1 8-23 CO2CH3 CH2CH2 SO 2 CF3 152 8-24 cyclopropyl CH2CH2 SO21 CF3 19F: −63.6, −78.3 8-25 CH2CH═CH2 CH2CH2CH2 S 2 CF3 103-106 8-26CH2CH═CH2 CH2CH2 S 2 CF3 117-120 8-27 cyclobutyl CH2CH2 S 1 CF3 8-28CH2C≡CH CH2CH2 S 1 CF3 8-29 CH2C≡CH CH2CH2 S 2 CF3 89-92 8-30cyclopropyl CH2CH2 SO 2 CF2H 8-31 CH3 CH2CH2 S 2 CF2Cl 8-32 cyclopropylCH2CH2 SO 1 CFCl2 8-33 CH2CH3 CH2CH2 SO2 0 CF2Br 8-34 CO2CH2CH3CH2CH2CH2 SO 2 CF2Cl 8-35 CH2cyclopropyl CH2CH2 S 2 CF2Cl 8-36CH2cyclopropyl CH2CH2 S 2 CF2H 8-37 cyclopropyl CH2CH2 S 2 CF2Br 8-38CH2C≡CH CH2CH2CH2 S 1 CF2Cl 8-39 cyclopropyl CH2CH2 SO2 2 CF2Cl 8-40CH2CH3 CH2CH2 SO2 2 CF3 19F: −64.2, −78.8 8-41 cyclopropyl CH2CH2 SO2 2CF3 155 8-42 cyclopropyl CH2CH2 SO 2 CF3 164-166 8-43 CO-(2-THF) CH2CH2S 0 CF3 135 8-44 CO-(2-THF) CH2CH2 S 2 CF3 127 8-45 CO-(2-THF) CH2CH2CH2S 2 CF3 19F: −64.2, −80.9 8-46 COCH2OCH3 CH2CH2 S 2 CF3 8-47 COCH2OCH3CH2CH2 S 1 CF3 140 8-48 OCH3 CH2CH2 S 2 CF3 135 8-49 OPh CH2CH2CH2 S 2CF3 8-50 O(3-pyridyl) CH2CH2 S 1 CF3 8-51 CO(2-THF) CH2CH2 S 1 CF3 8-52OCH2CH3 CH2CH2 SO2 1 CF3 8-53 OCH3 CH2CH2 SO 2 CF3 137 8-54 OCH3 CH2CH2SO2 2 CF3 159 8-55 COCH2OEt CH2CH2 S 1 CF3 52 8-56 COCH2OEt CH2CH2 S 2CF3 19F: −64.3, −81.0 8-57 CO-(2-THF) CH2CH2 SO2 2 CF3 8-58 CO-(2-THF)CH2CH2 SO2 0 CF3 8-59 COCH2OCH3 CH2CH2 S 0 CF3 gum 8-60 CO-(2-THF)CH2CH2 SO 2 CF3

TABLE IX R¹ = CN; R² = Cl; W = C—Cl; R³ = CF₃; R⁶ = CF₃: Cpd m.p. (°C.); or No R⁴ A S(O)_(m) R⁵ n NMR (ppm) 9-1 COOnC4H9 CH2CH2 S Ph 0 19F:−42.2; −63.7 9-2 COOiPr CH2CH2 S Ph 0 19F: −42.5; −64.2 9-3 COOPh CH2CH2SO2 Ph 1 9-4 COO-(4-OMe—Ph) CH2CH2 S CH3 2 19F: −63.7; −77.5 9-5 COOCH3CH2CH2 S CH3 0 9-6 COOCH3 CH2CH2 S CH3 1 9-7 CH2cyclopropyl CH2CH2 SO2CH3 2 9-8 COOCH3 CH2CH2 SO CH3 0 9-9 COOCH3 CH2CH2 SO CH3 1 9-10CH2CH═CH2 CH2CH2 SO2 CH3 2 141 9-11 COOCH3 CH2CH2 SO2 CH3 0 9-12 COOCH3CH2CH2 SO2 CH3 1 9-13 COOCH3 CH2CH2 SO2 CH3 2 9-14 COOnPr CH2CH2 S CH3 09-15 COOnPr CH2CH2 S CH3 1 9-16 COOnPr CH2CH2 S CH3 2 9-17 COOnPr CH2CH2SO CH3 0 9-18 COOnPr CH2CH2 SO CH3 1 9-19 COOnPr CH2CH2 SO CH3 2 9-20COOnPr CH2CH2 SO2 CH3 0 9-21 COOnPr CH2CH2 SO2 CH3 1 9-22 COOnPr CH2CH2SO2 CH3 2 9-23 COOiPr CH2CH2 S CH3 0 9-24 COOiPr CH2CH2 S CH3 1 9-25COOiPr CH2CH2 S CH3 2 9-26 COOiPr CH2CH2 SO CH3 0 9-27 COOiPr CH2CH2 SOCH3 1 9-28 COOiPr CH2CH2 SO CH3 2 9-29 COOiPr CH2CH2 SO2 CH3 0 9-30COOiPr CH2CH2 SO2 CH3 1 9-31 COOiPr CH2CH2 SO2 CH3 2 9-32 COOnBu CH2CH2S CH3 0 9-33 COOnBu CH2CH2 S CH3 1 9-34 COOnBu CH2CH2 S CH3 2 9-35COOnBu CH2CH2 SO CH3 0 9-36 COOnBu CH2CH2 SO CH3 1 9-37 COOnBu CH2CH2 SOCH3 2 9-38 COOnBu CH2CH2 SO2 CH3 0 9-39 COOnBu CH2CH2 SO2 CH3 1 9-40COOnBu CH2CH2 SO2 CH3 2 9-41 COOCH3 CH2CH2CH2 S CH3 0 9-42 COOCH3CH2CH2CH2 S CH3 1 9-43 COOCH3 CH2CH2CH2 S CH3 2 9-44 COOCH3 CH2CH2CH2 SOCH3 0 9-45 COOCH3 CH2CH2CH2 SO CH3 1 9-46 CH2C≡CH CH2CH2 SO2 CH3 2 9-47COOCH3 CH2CH2CH2 SO2 CH3 0 9-48 COOCH3 CH2CH2CH2 SO2 CH3 1 9-49 COOCH3CH2CH2CH2 SO2 CH3 2 9-50 COOnPr CH2CH2CH2 S CH3 0 9-51 COOnPr CH2CH2CH2S CH3 1 9-52 COOnPr CH2CH2CH2 S CH3 2 9-53 COOnPr CH2CH2CH2 SO CH3 09-54 COOnPr CH2CH2CH2 SO CH3 1 9-55 COOnPr CH2CH2CH2 SO CH3 2 9-56COOnPr CH2CH2CH2 SO2 CH3 0 9-57 COOnPr CH2CH2CH2 SO2 CH3 1 9-58 COOnPrCH2CH2CH2 SO2 CH3 2 9-59 COOiPr CH2CH2CH2 S CH3 0 9-60 COOiPr CH2CH2CH2S CH3 1 9-61 COOiPr CH2CH2CH2 S CH3 2 9-62 COOiPr CH2CH2CH2 SO CH3 09-63 COOiPr CH2CH2CH2 SO CH3 1 9-64 COOiPr CH2CH2CH2 SO CH3 2 9-65COOiPr CH2CH2CH2 SO2 CH3 0 9-66 COOiPr CH2CH2CH2 SO2 CH3 1 9-67 COOiPrCH2CH2CH2 SO2 CH3 2 9-68 COOnBu CH2CH2CH2 S CH3 0 9-69 COOnBu CH2CH2CH2S CH3 1 9-70 COOnBu CH2CH2CH2 S CH3 2 9-71 COOnBu CH2CH2CH2 SO CH3 09-72 COOnBu CH2CH2CH2 SO CH3 1 9-73 COOnBu CH2CH2CH2 SO CH3 2 9-74COOnBu CH2CH2CH2 SO2 CH3 0 9-75 COOnBu CH2CH2CH2 SO2 CH3 1 9-76 COOnBuCH2CH2CH2 SO2 CH3 2 9-77 COOPh CH2CH2 S CH3 0 9-78 COOPh CH2CH2 S CH3 19-79 COOPh CH2CH2 S CH3 2 9-80 COOPh CH2CH2 SO CH3 0 9-81 COOPh CH2CH2SO CH3 1 9-82 COOPh CH2CH2 SO CH3 2 9-83 COOPh CH2CH2 SO2 CH3 0 9-84COOPh CH2CH2 SO2 CH3 1 9-85 COOPh CH2CH2 SO2 CH3 2 9-86 COOCH2Ph CH2CH2S CH3 0 9-87 COOCH2Ph CH2CH2 S CH3 1 9-88 COOCH2Ph CH2CH2 S CH3 2 9-89COOCH2Ph CH2CH2 SO CH3 0 9-90 COOCH2Ph CH2CH2 SO CH3 1 9-91 COOCH2PhCH2CH2 SO CH3 2 9-92 COOCH2Ph CH2CH2 SO2 CH3 0 9-93 COOCH2Ph CH2CH2 SO2CH3 1 9-94 COOCH2Ph CH2CH2 SO2 CH3 2 9-95 COCH3 CH2CH2 S CH3 0 9-96COCH3 CH2CH2 S CH3 1 9-97 COCH3 CH2CH2 S CH3 2 9-98 COCH3 CH2CH2 SO CH30 9-99 COCH3 CH2CH2 SO CH3 1 9-100 COCH3 CH2CH2 SO CH3 2 9-101 COCH3CH2CH2 SO2 CH3 0 9-102 COCH3 CH2CH2 SO2 CH3 1 9-103 COCH3 CH2CH2 SO2 CH32 9-104 CH2CH═CH2 CH2CH2 S CH3 0 19F: −44.2, −64.1 9-105 CH2CH═CH2CH2CH2 SO CH3 1 9-106 CH2C≡CH CH2CH2 S CH3 0 65 9-107 CH2C≡CH CH2CH2 SOCH3 1 9-108 CH2cyclopropyl CH2CH2 S CH3 0 72 9-109 CH2cyclopropyl CH2CH2SO CH3 1 9-110 cyclobutyl CH2CH2 S CH3 2 116 9-111 cyclobutyl CH2CH2 SOCH3 2 150 9-112 cyclobutyl CH2CH2 SO2 CH3 2 167

TABLE X Compounds of formula (Ia): (Ia)

Cpd Number R⁴ R⁵ r n m.p.(° C.) 10-1 H CH3 1 0 10-2 H CH3 1 1 10-3 H CH31 2 10-4 CH3 CH3 1 0 10-5 CH3 CH3 1 1 10-6 CH3 CH3 1 2 10-7 CH3 Et 1 010-8 CH3 Et 1 1 10-9 CH3 Et 1 2 10-10 CH3 CH2CH═CH2 1 0 10-11 CH3CH2CH═CH2 1 1 10-12 CH3 CH2CH═CH2 1 2 10-13 CH3 CH2Ph 1 1 10-14 CH3 Ph 11 10-15 Et CH3 1 0 10-16 Et CH3 1 1 10-17 Et CH3 1 2 10-18 CH2CH═CH2 CH31 0 10-19 CH2CH═CH2 CH3 1 1 10-20 CH2CH═CH2 CH3 1 2 10-21 CH2C≡CH CH3 10 10-22 CH2C≡CH CH3 1 1 10-23 CH2C≡CH CH3 1 2 10-24 C(O)OEt CH3 1 010-25 C(O)OEt CH3 1 1 10-26 C(O)OEt CH3 1 2 10-27 CH2cyclopropyl CH3 1 010-28 CH2cyclopropyl CH3 1 1 10-29 CH2cyclopropyl CH3 1 2 10-30 H CH3 20 10-31 H CH3 2 1 10-32 H CH3 2 2 10-33 CH3 CH3 2 0 10-34 CH3 CH3 2 110-35 CH3 CH3 2 2 10-36 CH3 Et 2 0 10-37 CH3 Et 2 1 10-38 CH3 Et 2 210-39 CH3 CH2CH═CH2 2 0 10-40 CH3 CH2CH═CH2 2 1 10-41 CH3 CH2CH═CH2 2 210-42 CH3 CH2Ph 2 1 10-43 CH3 Ph 2 1 10-44 Et CH3 2 0 10-45 Et CH3 2 110-46 Et CH3 2 2 10-47 CH2CH═CH2 CH3 2 0 10-48 CH2CH═CH2 CH3 2 1 10-49CH2CH═CH2 CH3 2 2 10-50 CH2C≡CH CH3 2 0 10-51 CH2C≡CH CH3 2 1 10-52CH2C≡CH CH3 2 2 10-53 C(O)OEt CH3 2 0 10-54 C(O)OEt CH3 2 1 10-55C(O)OEt CH3 2 2 10-56 CH2cyclopropyl CH3 2 0 10-57 CH2cyclopropyl CH3 21 10-58 CH2cyclopropyl CH3 2 2 10-59 H CH3 3 0 10-60 H CH3 3 1 10-61 HCH3 3 2 10-62 CH3 CH3 3 0 10-63 CH3 CH3 3 1 10-64 CH3 CH3 3 2 10-65 CH3Et 3 0 10-66 CH3 Et 3 1 10-67 CH3 Et 3 2 10-68 CH3 CH2CH═CH2 3 0 10-69CH3 CH2CH═CH2 3 1 10-70 CH3 CH2CH═CH2 3 2 10-71 CH3 CH2Ph 3 1 10-72 CH3Ph 3 1 10-73 Et CH3 3 0 10-74 Et CH3 3 1 10-75 Et CH3 3 2 10-76CH2CH═CH2 CH3 3 0 10-77 CH2CH═CH2 CH3 3 1 10-78 CH2CH═CH2 CH3 3 2 10-79CH2C≡CH CH3 3 0 10-80 CH2C≡CH CH3 3 1 10-81 CH2C≡CH CH3 3 2 10-82C(O)OEt CH3 3 0 10-83 C(O)OEt CH3 3 1 10-84 C(O)OEt CH3 3 2 10-85CH2cyclopropyl CH3 3 0 10-86 CH2cyclopropyl CH3 3 1 10-87 CH2cyclopropylCH3 3 2 10-88 CH3 CH3 4 0 10-89 CH3 CH3 4 1 10-90 CH3 CH3 4 2 10-91 CH3Et 4 0 10-92 CH3 Et 4 1 10-93 CH3 Et 4 2

TABLE XI Compounds of formula (Ib): (Ib)

Cpd Number R⁴ R⁵ r n m.p.(° C.) 11-1 H CH3 1 0 11-2 H CH3 1 1 11-3 H CH31 2 11-4 CH3 CH3 1 0 11-5 CH3 CH3 1 1 11-6 CH3 CH3 1 2 11-7 CH3 Et 1 011-8 CH3 Et 1 1 11-9 CH3 Et 1 2 11-10 CH3 CH2CHCH2 1 0 11-11 CH3CH2CHCH2 1 1 11-12 CH3 CH2CHCH2 1 2 11-13 CH3 CH2Ph 1 1 11-14 CH3 Ph 1 111-15 Et CH3 1 0 11-16 Et CH3 1 1 11-17 Et CH3 1 2 11-18 CH2CHCH2 CH3 10 11-19 CH2CHCH2 CH3 1 1 11-20 CH2CHCH2 CH3 1 2 11-21 CH2CCH CH3 1 011-22 CH2CCH CH3 1 1 11-23 CH2CCH CH3 1 2 11-24 C(O)OEt CH3 1 0 11-25C(O)OEt CH3 1 1 11-26 C(O)OEt CH3 1 2 11-27 CH2cyclopropyl CH3 1 0 11-28CH2cyclopropyl CH3 1 1 11-29 CH2cyclopropyl CH3 1 2 11-30 H CH3 2 011-31 H CH3 2 1 11-32 H CH3 2 2 11-33 CH3 CH3 2 0 11-34 CH3 CH3 2 111-35 CH3 CH3 2 2 11-36 CH3 Et 2 0 11-37 CH3 Et 2 1 11-38 CH3 Et 2 211-39 CH3 CH2CHCH2 2 0 11-40 CH3 CH2CHCH2 2 1 11-41 CH3 CH2CHCH2 2 211-42 CH3 CH2Ph 2 1 11-43 CH3 Ph 2 1 11-44 Et CH3 2 0 11-45 Et CH3 2 111-46 Et CH3 2 2 11-47 CH2CHCH2 CH3 2 0 11-48 CH2CHCH2 CH3 2 1 11-49CH2CHCH2 CH3 2 2 11-50 CH2CCH CH3 2 0 11-51 CH2CCH CH3 2 1 11-52 CH2CCHCH3 2 2 11-53 C(O)OEt CH3 2 0 11-54 C(O)OEt CH3 2 1 11-55 C(O)OEt CH3 22 11-56 CH2cyclopropyl CH3 2 0 11-57 CH2cyclopropyl CH3 2 1 11-58CH2cyclopropyl CH3 2 2 11-59 H CH3 3 0 11-60 H CH3 3 1 11-61 H CH3 3 211-62 CH3 CH3 3 0 11-63 CH3 CH3 3 1 11-64 CH3 CH3 3 2 11-65 CH3 Et 3 011-66 CH3 Et 3 1 11-67 CH3 Et 3 2 11-68 CH3 CH2CHCH2 3 0 11-69 CH3CH2CHCH2 3 1 11-70 CH3 CH2CHCH2 3 2 11-71 CH3 CH2Ph 3 1 11-72 CH3 Ph 3 111-73 Et CH3 3 0 11-74 Et CH3 3 1 11-75 Et CH3 3 2 11-76 CH2CHCH2 CH3 30 11-77 CH2CHCH2 CH3 3 1 11-78 CH2CHCH2 CH3 3 2 11-79 CH2CCH CH3 3 011-80 CH2CCH CH3 3 1 11-81 CH2CCH CH3 3 2 11-82 C(O)OEt CH3 3 0 11-83C(O)OEt CH3 3 1 11-84 C(O)OEt CH3 3 2 11-85 CH2cyclopropyl CH3 3 0 11-86CH2cyclopropyl CH3 3 1 11-87 CH2cyclopropyl CH3 3 2 11-88 CH3 CH3 4 011-89 CH3 CH3 4 1 11-90 CH3 CH3 4 2 11-91 CH3 Et 4 0 11-92 CH3 Et 4 111-93 CH3 Et 4 2

TABLE XII Compounds of formula (Ic): (Ic)

Cpd Number R⁴ R⁵ r n m.p.(° C.) 12-1 H CH3 1 0 12-2 H CH3 1 1 12-3 H CH31 2 12-4 CH3 CH3 1 0 12-5 CH3 CH3 1 1 12-6 CH3 CH3 1 2 12-7 CH3 Et 1 012-8 CH3 Et 1 1 12-9 CH3 Et 1 2 12-10 CH3 CH2CHCH2 1 0 12-11 CH3CH2CHCH2 1 1 12-12 CH3 CH2CHCH2 1 2 12-13 CH3 CH2Ph 1 1 12-14 CH3 Ph 1 112-15 Et CH3 1 0 12-16 Et CH3 1 1 12-17 Et CH3 1 2 12-18 CH2CHCH2 CH3 10 12-19 CH2CHCH2 CH3 1 1 12-20 CH2CHCH2 CH3 1 2 12-21 CH2CCH CH3 1 012-22 CH2CCH CH3 1 1 12-23 CH2CCH CH3 1 2 12-24 C(O)OEt CH3 1 0 12-25C(O)OEt CH3 1 1 12-26 C(O)OEt CH3 1 2 12-27 CH2cyclopropyl CH3 1 0 12-28CH2cyclopropyl CH3 1 1 12-29 CH2cyclopropyl CH3 1 2 12-30 H CH3 2 012-31 H CH3 2 1 12-32 H CH3 2 2 12-33 CH3 CH3 2 0 12-34 CH3 CH3 2 112-35 CH3 CH3 2 2 12-36 CH3 Et 2 0 12-37 CH3 Et 2 1 12-38 CH3 Et 2 212-39 CH3 CH2CHCH2 2 0 12-40 CH3 CH2CHCH2 2 1 12-41 CH3 CH2CHCH2 2 212-42 CH3 CH2Ph 2 1 12-43 CH3 Ph 2 1 12-44 Et CH3 2 0 12-45 Et CH3 2 112-46 Et CH3 2 2 12-47 CH2CHCH2 CH3 2 0 12-48 CH2CHCH2 CH3 2 1 12-49CH2CHCH2 CH3 2 2 12-50 CH2CCH CH3 2 0 12-51 CH2CCH CH3 2 1 12-52 CH2CCHCH3 2 2 12-53 C(O)OEt CH3 2 0 12-54 C(O)OEt CH3 2 1 12-55 C(O)OEt CH3 22 12-56 CH2cyclopropyl CH3 2 0 12-57 CH2cyclopropyl CH3 2 1 12-58CH2cyclopropyl CH3 2 2 12-59 H CH3 3 0 12-60 H CH3 3 1 12-61 H CH3 3 212-62 CH3 CH3 3 0 12-63 CH3 CH3 3 1 12-64 CH3 CH3 3 2 12-65 CH3 Et 3 012-66 CH3 Et 3 1 12-67 CH3 Et 3 2 12-68 CH3 CH2CHCH2 3 0 12-69 CH3CH2CHCH2 3 1 12-70 CH3 CH2CHCH2 3 2 12-71 CH3 CH2Ph 3 1 12-72 CH3 Ph 3 112-73 Et CH3 3 0 12-74 Et CH3 3 1 12-75 Et CH3 3 2 12-76 CH2CHCH2 CH3 30 12-77 CH2CHCH2 CH3 3 1 12-78 CH2CHCH2 CH3 3 2 12-79 CH2CCH CH3 3 012-80 CH2CCH CH3 3 1 12-81 CH2CCH CH3 3 2 12-82 C(O)OEt CH3 3 0 12-83C(O)OEt CH3 3 1 12-84 C(O)OEt CH3 3 2 12-85 CH2cyclopropyl CH3 3 0 12-86CH2cyclopropyl CH3 3 1 12-87 CH2cyclopropyl CH3 3 2 12-88 CH3 CH3 4 012-89 CH3 CH3 4 1 12-90 CH3 CH3 4 2 12-91 CH3 Et 4 0 12-92 CH3 Et 4 112-93 CH3 Et 4 2

The term “compound of the invention” as used hereinafter embraces a5-substituted-alkylaminopyrazole of formula (I) as defined above and apesticidally acceptable salt thereof.

In a preferred aspect of the invention the compounds of formula (I) areused for the control of parasites of animals. Preferably the animal tobe treated is a domestic companion animal such as a dog or a cat.

In a further aspect of the invention the compounds of formula (I) orsalts or compositions thereof are used for the preparation of aveterinary medicament, preferably for the control of parasites,specifically ecto and endo parasites, in and on animals.

The compounds of the invention and methods of use thereof are ofparticular value in the control of arthropods or helminths which areinjurious to, or spread or act as vectors of diseases domestic animals,for example those hereinbefore mentioned, and more especially in thecontrol of ticks, mites, lice, fleas, midges, or biting, nuisance ormyiasis flies. The compounds of the invention are particularly useful incontrolling arthropods or helminths which are present inside domestichost animals or which feed in or on the skin or suck the blood of theanimal, for which purpose they may be administered orally, parenterally,percutaneously or topically.

The compositions hereinafter described may, in general, be employed toanimals infested by or exposed to infestation by arthropods orhelminths, by parenteral, oral or topical application of compositions inwhich the active ingredient exhibits an immediate and/or prolongedaction over a period of time against the arthropods or helminths, forexample by incorporation in feed or suitable orally-ingestiblepharmaceutical formulations, edible baits, salt licks, dietarysupplements, pour-on formulations, sprays, baths, dips, showers, jets,dusts, greases, shampoos, creams, wax smears or livestock self-treatmentsystems;

The compounds of formula (I) are particularly useful for the control ofparasites of animals when applied orally, and in a further preferredaspect of the invention the compounds of formula (I) are used for thecontrol of parasites of animals by oral application. The compounds ofthe formula (I) or salts thereof may be administered before, during orafter meals. The compounds of the formula (I) or salts thereof may bemixed with a carrier and/or foodstuff.

The compound of the formula (I) or salt thereof is administered orallyin a dose to the animal in a dose range generally from 0.1 to 500 mg/kgof the compound of the. formula (I) or salt thereof per kilogram ofanimal body weight (mg/kg).

The frequency of treatment of the animal, preferably the domestic animalto be treated by the compound of the formula (I) or salt thereof isgenerally from about once per week to about once per year, preferablyfrom about once every two weeks to once every three months.

The compounds of the invention may be administered most advantageouslywith another parasiticidally effective material, such as anendoparasiticide, and/or an ectoparasiticide, and/or anendectoparasiticide. For example, such compounds include macrocycliclactones such as avermectins or milbemycins e.g., ivermectin, pyratel oran insect growth regulator such as lufenuron or methoprene.

According to a further feature of the present invention there isprovided a method for the control of pests at a locus which comprisesthe application of an effective amount of a compound of formula (I).or asalt thereof. For this purpose, the said compound is normally used inthe form of a pesticidal composition (i.e. in association withcompatible diluents or carriers and/or surface active agents suitablefor use in pesticidal compositions), for example as hereinafterdescribed.

One aspect of the present invention as defined above is a method for thecontrol of pests at a locus. The locus includes, for example, the pestitself, the place (plant, field, forest, orchard, waterway, soil, plantproduct, or the like) where the pest resides or feeds, or a placesusceptible to future infestation by the pest. The compound of theinvention may therefore be applied directly to the pest, to the placewhere the pest resides or feeds, or to the place susceptible to futureinfestation by the pest. As is evident from the foregoing pesticidaluses, the present invention provides pesticidally active compounds andmethods of use of said compounds for the control of a number of pestspecies which includes: arthropods, especially insects or mites, orplant nematodes. The compound of the invention may thus beadvantageously employed in practical uses, for example, in veterinarymedicine or livestock husbandry, in agricultural or horticultural crops,in forestry, or in public health. The compounds of the invention may beused for example in the following applications and on the followingpests:

In the field of veterinary medicine or livestock husbandry or in themaintenance of, public health against arthropods which are parasiticinternally or externally upon vertebrates, particularly warm-bloodedvertebrates, for example domestic animals, e.g. cattle, sheep, goats,equines, swine, poultry, dogs or cats, for example Acarina, includingticks (e.g. sot-bodied ticks including Argasidae spp. e.g. Argas spp.and Ornithodorus spp. (e.g. Ornithodorus moubata); hard-bodied ticksincluding Ixodidae spp., e.g. Boophilus spp. e.g. Boophilus microplus,Rhipicephalus spp. e.g. Rhipicephalus appendiculatus and Rhipicephalussanguineus; mites (e.g. Damalinia spp.); fleas (e.g. Ctenocephalidesspp. e.g. Ctenocephalides felis (cat flea) and Ctenocephalides canis(dog flea)); lice e.g. Menopon spp.; Diptera (e.g. Aedes spp., Anophelesspp., Musca spp., Hypoderma spp.); Hemiptera; Dictyoptera (e.g.Periplaneta spp., Blatella spp.); Hymenoptera; for example againstinfections of the gastro-intestinal tract caused by parasitic nematodeworms, for example members of the family Trichostrongylidae.

For the control of soil insects, such as corn rootworm, termites(especially for protection of structures), root maggots, wireworms, rootweevils, stalkborers, cutworms, root aphids, or grubs. They may also beused to provide activity against plant pathogenic nematodes, such asroot-knot, cyst, dagger, lesion, or stem or bulb nematodes, or againstmites. For the control of soil pests, for example corn rootworm, thecompounds are advantageously applied to or incorporated at an effectiverate into the soil in which crops are planted or to be planted or to theseeds or growing plant roots.

In the area of public health, the compounds are especially useful in thecontrol of many insects, especially filth flies or other Dipteran pests,such as houseflies, stableflies, soldierflies, hornflies, deerflies,horseflies, midges, punkies, blackflies, or mosquitoes.

In the protection of stored products, for example cereals, includinggrain or flour, groundnuts, animal feedstuffs, timber or householdgoods, e.g. carpets and textiles, compounds of the invention are usefulagainst attack by arthropods, more especially beetles, includingweevils, moths or mites, for example. Ephestia spp. (flour moths),Anthrenus spp. (carpet beetles), Tribolium spp. (flour beetles),Sitophilus spp. (grain weevils) or Acarus spp. (mites).

In the control of cockroaches, ants or termites or similar arthropodpests in infested domestic or industrial premises or in the control ofmosquito larvae in waterways, wells, reservoirs or other running orstanding water.

For the treatment of foundations, structures or soil in the preventionof the attack on building by termites, for example, Reticulitermes spp.,Heterotermes spp., Coptotermes spp.

In agriculture against adults, larvae and eggs of Lepidoptera(butterflies and moths), e.g. Heliothis spp. such as Heliothis virescens(tobacco budworm), Heliothis armigera and Heliothis zea. Against adultsand larvae of Coleoptera (beetles) e.g. Anthonomus spp. e.g. grandis(cotton boll weevil), Leptinotarsa decemlineata (Colorado potatobeetle), Diabrotica spp. (corn rootworms). Against Heteroptera(Hemiptera and Homoptera) e.g. Psylla spp., Bemisia spp., Trialeurodesspp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp.,Nephotettix spp. (rice leaf hoppers), Nilaparvata spp.

Against Diptera e.g. Musca spp. Against Thysanoptera such as Thripstabaci. Against Orthoptera such as Locusta and Schistocerca spp.,(locusts and crickets) e.g. Gryllus spp., and Acheta spp. for example,Blatta orientalis, Periplaneta americana, Blatella germanica, Locustamigratoria migratorioides, and Schistocerca gregaria. Against Collembolae.g. Periplaneta spp. and Blatella spp. (roaches). Against arthropods ofagricultural significance such as Acari (mites) e.g. Tetranychus spp.,and Panonychus spp.

Against nematodes which attack plants or trees of importance toagriculture, forestry or horticulture either directly or by spreadingbacterial, viral, mycoplasma or fungal diseases of the plants. Forexample root-knot nematodes such as Meloidogyne spp. (e.g. M.incognita).

In practical use for the control of arthropods, especially insects ormites, or nematode pests of plants, a method, for example, comprisesapplying to the plants or to the medium in which they grow an effectiveamount of a compound of the invention. For such a method, the compoundof the invention is generally applied to the locus in which thearthropod or nematode infestation is to be controlled at an effectiverate in the range of about 2 g to about 1 kg of the active compound perhectare of locus treated. Under ideal conditions, depending on the pestto be controlled, a lower rate may offer adequate protection. On theother hand, adverse weather conditions, resistance of the pest or otherfactors may require that the active ingredient be used at higher rates.The optimum rate depends usually upon a number of factors, for example,the type of pest being controlled, the type or the growth stage of theinfested plant, the row spacing or also the method of application.Preferably an effective rate range of the active compound is from about10 g/ha to about 400 g/ha, more preferably from about 50 g/ha to about200 g/ha.

When a pest is soil-borne, the active, compound generally in aformulated composition, is distributed evenly over the area to betreated (i.e., for example broadcast or band treatment) in anyconvenient manner and is applied at rates from about 10 g/ha to about400 g ai/ha, preferably from about 50 g/ha to about 200 g ai/ha. Whenapplied as a root dip to seedlings or drip irrigation to plants theliquid solution or suspension contains from about 0.075 to about 1000 mgai/l, preferably from about 25 to about 200 mg ai/l. Application may bemade, if desired, to the field or crop-growing area generally or inclose proximity to the seed or plant to be protected from attack. Thecompound of the invention can be washed into the soil by spraying withwater over the area or can be left to the natural action of rainfall.During or after application, the formulated compound can, if desired, bedistributed mechanically in the soil, for example by ploughing, disking,or use of drag chains. Application can be prior to planting, atplanting, after planting but before sprouting has taken place, or aftersprouting.

The compound of the invention and methods of control of pests therewithare of particular value in the protection of field, forage, plantation,glasshouse, orchard or vineyard crops, of ornamentals, or of plantationor forest trees, for example: cereals (such as wheat or rice), cotton,vegetables (such as peppers), field crops (such as sugar beets, soybeansor oil seed rape), grassland or forage crops (such as maize or sorghum),orchards or groves (such as of stone or pit fruit or citrus), ornamentalplants, flowers or vegetables or shrubs under glass or in gardens orparks, or forest trees (both deciduous and evergreen) in forests,plantations or nurseries. They are also valuable in the protection oftimber (standing, felled, converted, stored or structural) from attack,for example, by sawflies or beetles or termites. They have applicationsin the protection of stored products such as grains, fruits, nuts,spices or tobacco, whether whole, milled or compounded into products,from moth, beetle, mite or grain weevil attack. Also protected arestored animal products such as skins, hair, wool or feathers in naturalor converted form (e.g. as carpets or textiles) from moth or beetleattack as well as stored meat, fish or grains from beetle, mite or flyattack.

The compositions hereinafter described for application to growing cropsor crop growing loci or as a seed dressing may, in general,alternatively be employed in the protection of stored products,household goods, property or areas of the general environment. Suitablemeans of applying the compounds of the invention include: to growingcrops as foliar sprays (for example as an in-furrow spray), dusts,granules, fogs or foams or also as suspensions of finely divided orencapsulated compositions as soil or root treatments by liquid drenches,dusts, granules, smokes or foams; to seeds of crops via application asseed dressings by liquid slurries or dusts;

to the environment in general or to specific locations where pests maylurk, including stored products, timber, household goods, or domestic orindustrial premises, as sprays, fogs, dusts, smokes, wax-smears,lacquers, granules or baits, or in tricklefeeds to waterways, wells,reservoirs or other running or standing water.

The compounds of the formula (I) can also be employed for controllingharmful organisms in crops of known genetically engineered plants orgenetically engineered plants yet to be developed. As a rule, thetransgenic plants are distinguished by especially advantageousproperties, for example by resistances to particular crop protectionagents, resistances to plant diseases or pathogens of plant diseases,such as particular insects or microorganisms such as fungi, bacteria orviruses. Other particular properties concern, for example, the harvestedmaterial with regard to quantity, quality, storage properties,composition and specific constituents. Thus, transgenic plants are knownwhere the starch content is increased, or the starch quality is altered,or where the harvested material has a different fatty acid composition.

The use in economically important transgenic crops of useful plants andornamentals is preferred, for example of cereals such as wheat, barley,rye, oats, millet, rice, cassava and maize or else crops of sugar beet,cotton, soya, oilseed rape, potatoes, tomatoes, peas and other types ofvegetables.

When used in transgenic crops, in particular those which haveresistances to insects, effects are frequently, observed, in addition tothe effects against harmful organisms to be observed in other crops,which are specific for application in the transgenic crop in question,for example an altered or specifically widened spectrum of pests whichcan be controlled, or altered application rates which may be employedfor application.

The invention therefore also relates to the use of compounds of theformula (I) for controlling harmful organisms in transgenic crop plants.

According to a further feature of the present invention there isprovided a pesticidal composition comprising one or more compounds ofthe invention as defined above, in association with, and preferablyhomogeneously dispersed in one or more compatible pesticidallyacceptable diluents or carriers and/or surface active agents [i.e.diluents or carriers and/or surface active agents of the type generallyaccepted in the art as being suitable for use in pesticidal compositionsand which are compatible with compounds of the invention].

In practice, the compounds of the invention most frequently form partsof compositions. These compositions can be employed to controlarthropods, especially insects, or plant nematodes or mites. Thecompositions may be of any type known in the art suitable forapplication to the desired pest in any premises or indoor or outdoorarea. These compositions contain at least one compound of the inventionas the active ingredient in combination or association with one or moreother compatible components which are for example, solid or liquidcarriers or diluents, adjuvants, surface-active-agents, or the likeappropriate for the intended use and which are agronomically ormedicinally acceptable. These compositions, which may be prepared by anymanner known in the art, likewise form a part of this invention.

The compounds of the invention, in their commercially availableformulations and in the use forms prepared from these formulations maybe present in mixtures with other active substances such asinsecticides, attractants, sterilants, acaricides, nematicides,fungicides, growth regulatory substances or herbicides.

The pesticides include, for example, phosphoric esters, carbamates,carboxylic esters, formamidines, tin compounds and materials produced bymicroorganisms.

Preferred components in mixtures are:

1. From the Group of the Phosphorus Compounds

-   acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos,    bromophos-ethyl, cadusafos (F-67825), chlorethoxyphos,    chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl,    demeton, demeton-S-methyl, demeton-S-methyl sulfone, dialifos,    diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, EPN,    ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitriothion,    fensulfothion, fenthion, flupyrazofos, fonofos, formothion,    fosthiazate, heptenophos, isazophos, isothioate, isoxathion,    malathion, methacrifos, methamidophos, methidathion, salithion,    mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl,    parathion, parathion-methyl, phenthoate, phorate, phosalone,    phosfolan, phosphocarb (BAS-301), phosmet, phosphamidon, phoxim,    pirimiphos, pirimiphos-ethyl, pirimiphos-methyl, profenofos,    propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion,    quinalphos, sulprofos, temephos, terbufos, tebupirimfos,    tetrachlorvinphos, thiometon, triazophos, trichlorphon, vamidothion;    2. From the Group of the Carbamates-   alanycarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate    (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb,    ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl,    5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb,    propoxur, thiodicarb, thiofanox,    1-methylthio(ethylideneamino)-N-methyl-N-(morpholinothio)carbamate    (UC 51717), triazamate;    3. From the Group of the Carboxylic Esters-   acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl    (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate,    beta-cyfluthrin, alpha-cypermethrin, beta-cypermethrin,    bioallethrin, bioallethrin ((S)-cyclopentylisomer), bioresmethrin,    bifenthrin, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl    (1RS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate    (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythithrin,    cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate,    fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin,    fluvalinate (D isomer), imiprothrin (S-41311), lambda-cyhalothrin,    permethrin, phenothrin (® isomer), prallethrin, pyrethrins (natural    products), resmethrin, tefluthrin, tetramethrin, theta-cypermethrin,    tralomethrin, transfluthrin, zeta-cypermethrin (F-56701);    4. From the Group of the Amidines-   amitraz, chlordimeform;    5. From the Group of the Tin Compounds-   cyhexatin, fenbutatin oxide;    6. Others-   abamectin, ABG-9008, acetamiprid, acequinocyl, Anagrapha falcitera,    AKD-1022, AKD-3059, ANS-118, azadirachtin, Bacillus thuringiensis,    Beauveria bassianea, bensultap, bifenazate, binapacryl, BJL-932,    bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, cartap,    chlorobenzilate, chlorfenapyr, chlorfluazuron,    2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930),    chlorfentezine, chlorproxyfen, chromafenozide, clothianidine,    2-naphthylmethyl cyclopropanecarboxylate (Ro12-0470), cyromazin,    diacloden (thiamethoxam), diafenthiuron, DBI-3204, ethyl    2-chloro-N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-carboximidate,    DDT, dicofol, diflubenzuron,    N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)2,4-xylidine,    dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, diofenolan,    emamectin benzoate, endosulfan, ethiprole (sulfethiprole),    ethofenprox, etoxazole, fenazaquin, fenoxycarb, fipronil, fluazuron,    flumite (flufenzine, SZI-121),    2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI    800), granulosis and nuclear polyhedrosis viruses, fenpyroximate,    fenthiocarb, fluacrypyrim, flubenzimine, flubrocythrinate,    flucycloxuron, flufenoxuron, flufenzine, flufenprox, fluproxyfen,    gamma-HCH, halfenozide, halofenprox, hexaflumuron (DE_(—)473),    hexythiazox, HOI-9004, hydramethylnon (AC 217300), IKI-220,    indoxacarb, ivermectin, L-14165, imidacloprid, indoxacarb    (DPX-MP062), kanemite (AKD-2023), lufenuron, M-020, M-020,    methoxyfenozide, milbemectin, NC-196, neemgard, nidinoterfuran,    nitenpyram, 2-nitromethyl-4,5-dihydro-6H-thiazine (DS 52618),    2-nitromethyl-3,4-dihydrothiazole (SD 35651),    2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehyde (WL 108477),    novaluron, pirydaryl, propargite, protrifenbute, pymethrozine,    pyridaben, pyrimidifen, pyriproxyfen, NC-196, NC-1111, NNI-9768,    novaluron (MCW-275), OK-9701, OK-9601, OK-9602, OK-9802, R-195,    RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen,    silomadine (CG-177), spinosad, spirodiclofen, SU-9118, tebufenozide,    tebufenpyrad, teflubenzuron, tetradifon, tetrasul, thiacloprid,    thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn    A, triflumuron, verbutin, vertalec (mykotal), YI-5301.

The abovementioned components for combinations are known activesubstances, many of which are described in Ch. R Worthing, S. B. Walker,The Pesticide Manual, 12^(th) Edition, British Crop Protection Council,Farnham 2000.

The effective use doses of the compounds employed in the invention canvary within wide limits, particularly depending on the nature of thepest to be eliminated or degree of infestation, for example, of cropswith these pests. In general, the compositions according to theinvention usually contain about 0.05 to about 95% (by weight) of one ormore active ingredients according to the invention, about 1 to about 95%of one or more solid or liquid carriers and, optionally, about 0.1 toabout 50% of one or more other compatible components, such assurface-active agents or the like. In the present account, the term“carrier” denotes an organic or inorganic ingredient, natural orsynthetic, with which the active ingredient is combined to facilitateits application, for example, to the plant, to seeds or to the soil.This carrier is therefore generally inert and it must be acceptable (forexample, agronomically acceptable, particularly to the treated plant).

The carrier may be a solid, for example, clays, natural or syntheticsilicates, silica, resins, waxes, solid fertilizers (for exampleammonium salts), ground natural minerals, such as kaolins, clays, talc,chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceousearth, or ground synthetic minerals, such as silica, alumina, orsilicates especially aluminum or magnesium silicates. As solid carriersfor granules the following are suitable: crushed or fractionated naturalrocks such as calcite, marble, pumice, sepiolite and dolomite; syntheticgranules of inorganic or organic meals; granules of organic materialsuch as sawdust, coconut shells, corn cobs, corn husks or tobaccostalks; kieselguhr, tricalcium phosphate, powdered cork, or absorbentcarbon black; water soluble polymers, resins, waxes; or solidfertilizers. Such solid compositions may, if desired, contain one ormore compatible wetting, dispersing, emulsifying or coloring agentswhich, when solid, may also serve as a diluent.

The carrier may also be liquid, for example: water; alcohols,particularly butanol or glycol, as well as their ethers or esters,particularly methylglycol acetate; ketones, particularly acetone,cyclohexanone, methylethyl ketone, methylisobutylketone, or isophorone;petroleum fractions such as paraffinic or aromatic hydrocarbons,particularly xylenes or alkyl naphthalenes; mineral or vegetable oils,aliphatic chlorinated hydrocarbons, particularly trichloroethane ormethylene chloride; aromatic chlorinated hydrocarbons, particularlychlorobenzenes; water-soluble or strongly polar solvents such asdimethylformamide, dimethyl sulphoxide, or N-methylpyrrolidone;liquefied gases; or the like or a mixture thereof.

The surface-active agent may be an emulsifying agent, dispersing agentor wetting agent of the ionic or non-ionic type or a mixture of suchsurface-active agents. Amongst these are e.g., salts of polyacrylicacids, salts of lignosulphonic acids, salts of phenolsulphonic ornaphthalenesulphonic acids, polycondensates of ethylene oxide with fattyalcohols or fatty acids or fatty esters or fatty amines, substitutedphenols (particularly alkylphenols or arylphenols), salts ofsulphosuccinic acid esters, taurine derivatives (particularlyalkyltaurates), phosphoric esters of alcohols or of polycondensates ofethylene oxide with phenols, esters of fatty acids with polyols, orsulphate, sulphonate or phosphate functional derivatives of the abovecompounds. The presence of at least one surface-active agent isgenerally essential when the active ingredient and/or the inert carrierare only slightly water soluble or are not water soluble and the carrieragent of the composition for application is water. Compositions of theinvention may further contain other additives such as adhesives orcolorants. Adhesives such as carboxymethylcellulose or natural orsynthetic polymers in the form of powders, granules or lattices, such asarabic gum, polyvinyl alcohol or polyvinyl acetate, naturalphospholipids, such as cephalins or lecithins, or syntheticphospholipids can be used in the formulations. It is possible to usecolorants such as inorganic pigments, for example: iron oxides, titaniumoxides or Prussian Blue; organic dyestuffs, such as alizarin dyestuffs,azo dyestuffs or metal phthalocyanine dyestuffs; or trace nutrients suchas salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

For their agricultural application, the compounds of the invention aretherefore generally in the form of compositions, which are in varioussolid or liquid forms. Solid forms of compositions which can be used aredusting powders (with a content of the compound of the invention,ranging up to 80%), wettable powders or granules (including waterdispersible granules), particularly those obtained by extrusion,compacting, impregnation of a granular carrier, or granulation startingfrom a powder (the content of the compound of the invention, in thesewettable powders or granules being between about 0.5 and about 80%).Solid homogenous or heterogenous compositions containing one or morecompounds of the invention, for example granules, pellets, briquettes orcapsules, may be used to treat standing or running water over a periodof time. A similar effect may be achieved using trickle or intermittentfeeds of water dispersible concentrates as described herein.

Liquid compositions, for example, include aqueous or non-aqueoussolutions or suspensions (such as emulsifiable concentrates, emulsions,flowables, dispersions, or solutions) or aerosols. Liquid compositionsalso include, in particular, emulsifiable concentrates, dispersions,emulsions, flowables, aerosols, wettable powders (or powder forspraying), dry flowables or pastes as forms of compositions which areliquid or intended to form liquid compositions when applied, for exampleas aqueous sprays (including low and ultra-low volume) or as fogs oraerosols.

Liquid compositions, for example, in the form of emulsifiable or solubleconcentrates most frequently comprise about 5 to about 80% by weight ofthe active ingredient, while the emulsions or solutions which are readyfor application contain, in their case, about 0.01 to about 20% of theactive ingredient. Besides the solvent, the emulsifiable or solubleconcentrates may contain, when required, about 2 to about 50% ofsuitable additives, such as stabilizers, surface-active agents,penetrating agents, corrosion inhibitors, colorants or adhesives.Emulsions of any required concentration, which are particularly suitablefor application, for example, to plants, may be obtained from theseconcentrates by dilution with water. These compositions are includedwithin the scope of the compositions which may be employed in thepresent invention. The emulsions may be in the form of water-in-oil oroil-in-water type and they may have a thick consistency.

The liquid compositions of this invention may, in addition to normalagricultural use. applications be used for example to treat substratesor sites infested or liable to infestation by arthropods (or other pestscontrolled by compounds of this invention) including premises, outdooror indoor storage or processing areas, containers or equipment orstanding or running water.

All these aqueous dispersions or emulsions or spraying mixtures can beapplied, for example, to crops by any suitable means, chiefly byspraying, at rates which are generally of the order of about 100 toabout 1,200 liters of spraying mixture per hectare, but may be higher orlower (eg. low or ultra-low volume) depending upon the need orapplication technique. The compound or compositions according to theinvention are conveniently applied to vegetation and in particular toroots or leaves having pests to be eliminated. Another method ofapplication of the compounds or compositions according to the inventionis by chemigation, that is to say, the addition of a formulationcontaining the active ingredient to irrigation water. This irrigationmay be sprinkler irrigation for foliar pesticides or it can be groundirrigation or underground irrigation for soil or for systemicpesticides.

The concentrated suspensions, which can be applied by spraying, areprepared so as to produce a stable fluid product which does not settle(fine grinding) and usually contain from about 10 to about 75% by weightof active ingredient, from about 0.5 to about 30% of surface-activeagents, from about 0.1 to about 10% of thixotropic agents, from about 0to about 30% of suitable additives, such as anti-foaming agents,corrosion inhibitors, stabilizers, penetrating agents, adhesives and, asthe carrier, water or an organic liquid in which the active ingredientis poorly soluble or insoluble Some organic solids or inorganic saltsmay be dissolved in the carrier to help prevent settling or asantifreezes for water.

The wettable powers (or powder for spraying) are usually prepared sothat they contain from about 10 to about 80% by weight of activeingredient, from about 20 to about 90% of a solid carrier, from about 0to about 5% of a wetting agent, from about 3 to about 10% of adispersing agent and, when necessary, from about 0 to about 80% of oneor more stabilizers and/or other additives, such as penetrating agents,adhesives, anti-caking agents, colorants, or the like. To obtain thesewettable powders, the active ingredient is thoroughly mixed in asuitable blender with additional substances which may be impregnated onthe porous filler and is ground using a mill or other suitable grinder.This produces wettable powders, the wettability and the suspendabilityof which are advantageous. They may be suspended in water to give anydesired concentration and this suspension can be employed veryadvantageously in particular for application to plant foliage.

The “water dispersible granules (WG)” (granules which are readilydispersible in water) have compositions which are substantially close tothat of the wettable powders. They may be prepared by granulation offormulations described for the wettable powders, either by a wet route(contacting finely divided active ingredient with the inert filler and alittle water, e.g. 1 to 20% by weight, or with an aqueous solution of adispersing agent or binder, followed by drying and screening), or by adry route (compacting followed by grinding and screening).

The rates and concentrations of the formulated compositions may varyaccording to the method of application or the nature of the compositionsor use thereof. Generally speaking, the compositions for application tocontrol arthropod or plant nematode pests usually contain from about0.00001% to about 95%, more particularly from about 0.0005% to about 50%by weight of one or more compounds of the invention, or of total activeingredients (that is to say the compounds of the invention, togetherwith other substances toxic to arthropods or plant nematodes,synergists, trace elements or stabilizers). The actual compositionsemployed and their rate of application will be selected to achieve thedesired effect(s) by the farmer, livestock producer, medical orveterinary practitioner, pest control operator or other person skilledin the art.

Solid or liquid compositions for application topically to animals,timber, stored products or household goods usually contain from about0.00005% to about 90%, more particularly from about 0.001% to about 10%,by weight of one or more compounds of the invention. For administrationto animals orally or parenterally, including percutaneously solid orliquid compositions, these normally contain from about 0.1% to about 90%by weight of one or more compounds of the invention.

Medicated feedstuffs normally contain from about 0.001% to about 3% byweight of one or more compounds of the invention. Concentrates orsupplements for mixing with feedstuffs normally contain from about 5% toabout 90%, preferably from about 5% to about 50%, by weight of one ormore compounds of the invention. Mineral salt licks normally containfrom about 0.1% to about 10% by weight of one or more compounds offormula (I) or pesticidally acceptable salts thereof.

Dusts or liquid compositions for application to livestock, goods,premises or outdoor areas may contain from about 0.0001% to about 15%,more especially from about 0.005% to about 2.0%, by weight, of one ormore compounds of the invention.

Suitable concentrations in treated waters are between about 0.0001 ppmand about 20 ppm, more particularly about 0.001 ppm to about 5.0 ppm. ofone or more compounds of the invention, and may be used therapeuticallyin fish farming with appropriate exposure times. Edible baits maycontain from about 0.01% to about 5%, preferably from about 0.01% toabout 1.0%, by weight, of one or more compounds of the invention.

When administered to vertebrates parenterally, orally or by percutaneousor other means, the dosage of compounds of the invention, will dependupon the species, age, or health of the vertebrate and upon the natureand degree of its actual or potential infestation by arthropod orhelminth pests. A single dose of about 0.1 to about 100 mg, preferablyabout 2.0 to about 20.0 mg, per kg body weight of the animal or doses ofabout 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg, perkg body weight of the animal per day, for sustained medication, aregenerally suitable by oral or parenteral administration. By use ofsustained release formulations or devices, the daily doses required overa period of months may be combined and administered to animals on asingle occasion.

The following composition EXAMPLES 2A-2M illustrate compositions for useagainst arthropods, especially mites or insects, or plant nematodes,which comprise, as active ingredient, compounds of the invention, suchas those described in preparative examples. The compositions describedin EXAMPLES 2A-2M can each be diluted to give a sprayable composition atconcentrations suitable for use in the field. Generic chemicaldescriptions of the ingredients (for which all of the followingpercentages are in weight percent), used in the composition EXAMPLES2A-2M exemplified below, are as follows:

Trade Name Chemical Description Ethylan BCP Nonylphenol ethylene oxidecondensate Soprophor BSU Tristyrylphenol ethylene oxide condensateArylan CA A 70% w/v solution of calcium dodecylbenzenesulfonate Solvesso150 Light C₁₀ aromatic solvent Arylan S Sodium dodecylbenzenesulfonateDarvan NO₂ Sodium lignosulphonate Celite PF Synthetic magnesium silicatecarrier Sopropon T36 Sodium salts of polycarboxylic acids Rhodigel 23Polysaccharide xanthan gum Bentone 38 Organic derivative of magnesiummontmorillonite Aerosil Microfine silicon dioxide

Example 2A

A water soluble concentrate is prepared with the composition as follows:

Active ingredient  7% Ethylan BCP 10% N-methylpyrrolidone 83%

To a solution of Ethylan BCP dissolved in a portion ofN-methylpyrrolidone is added the active ingredient with heating andstirring until dissolved. The resulting solution is made up to volumewith the remainder of the solvent.

Example 2B

An emulsifiable concentrate (EC) is prepared with the composition asfollows:

Active ingredient 25%(max) Soprophor BSU 10% Arylan CA  5%N-methylpyrrolidone 50% Solvesso 150 10%

The first three components are dissolved in N-methylpyrrolidone and tothis is then added the Solvesso 150 to give the final volume.

Example 2C

A wettable powder (WP) is prepared with the composition as follows:

Active ingredient 40% Arylan S  2% Darvan NO₂  5% Celite PF 53%

The ingredients are mixed and ground in a hammer-mill to a powder with aparticle size of less than 50 microns.

Example 2D

An aqueous-flowable formulation is prepared with the composition asfollows:

Active ingredient 40.00%  Ethylan BCP 1.00% Sopropon T360. 0.20%Ethylene glycol 5.00% Rhodigel 230. 0.15% Water 53.65% 

The ingredients are intimately mixed and are ground in a bead mill untila mean particle size of less than 3 microns is obtained.

Example 2E

An emulsifiable suspension concentrate is prepared with the compositionas follows:

Active ingredient 30.0% Ethylan BCP 10.0% Bentone 38  0.5% Solvesso 15059.5%

The ingredients are intimately mixed and ground in a beadmill until amean particle size of less than 3 microns is obtained.

Example 2F

A water dispersible granule is prepared with the composition as follows:

Active ingredient 30% Darvan No 2 15% Arylan S  8% Celite PF 47%

The ingredients are mixed, micronized in a fluid-energy mill and thengranulated in a rotating pelletizer by spraying with water (up to 10%).The resulting granules are dried in a fluid-bed drier to remove excesswater.

Example 2G

A dusting powder is prepared with the composition as follows:

Active ingredient 1 to 10% Talc powder-superfine 99 to 90%

The ingredients are intimately mixed and further ground as necessary toachieve a fine powder. This powder may be applied to a locus ofarthropod infestation, for example refuse dumps, stored products orhousehold goods or animals infested by, or at risk of infestation by,arthropods to control the arthropods by oral ingestion. Suitable meansfor distributing the dusting powder to the locus of arthropodinfestation include mechanical blowers, handshakers or livestock selftreatment devices.

Example 2H

An edible bait is prepared with the composition as follows:

Active ingredient 0.1 to 1.0% Wheat flour 80% Molasses 19.9 to 19%

The ingredients are intimately mixed and formed as required into a baitform. This edible bait may be distributed at a locus, for exampledomestic or industrial premises, e.g. kitchens, hospitals or stores, oroutdoor areas, infested by arthropods, for example ants, locusts,cockroaches or flies, to control the arthropods by oral ingestion.

Example 2I

A solution formulation is prepared with a composition as follows:

Active ingredient 15% Dimethyl sulfoxide 85%

The active ingredient is dissolved in dimethyl sulfoxide with mixing andor heating as required. This solution may be applied percutaneously as apour-on application to domestic animals infested by arthropods or, aftersterilization by filtration through a polytetrafluoroethylene membrane(0.22 micrometer pore size), by parenteral injection, at a rate ofapplication of from 1.2 to 12 ml of solution per 100 kg of animal bodyweight.

Example 2J

A wettable powder is prepared with the composition as follows:

Active ingredient 50% Ethylan BCP  5% Aerosil  5% Celite PF 40%

The Ethylan BCP is absorbed onto the Aerosil which is then mixed withthe other ingredients and ground in a hammer-mill to give a wettablepowder, which may be diluted with water to a concentration of from0.001% to 2% by weight of the active compound and applied to a locus ofinfestation by arthropods, for example, dipterous larvae or plantnematodes, by spraying, or to domestic animals infested by, or at riskof infection by arthropods, by spraying or dipping, or by oraladministration in drinking water, to control the arthropods.

Example 2K

A slow release bolus composition is formed from granules containing thefollowing components in varying percentages(similar to those describedfor the previous compositions) depending upon need:

-   -   Active ingredient    -   Density agent    -   Slow-release agent    -   Binder

The intimately mixed ingredients are formed into granules which arecompressed into a bolus with a specific gravity of 2 or more. This canbe administered orally to ruminant domestic animals for retention withinthe reticulo-rumen to give a continual slow release of active compoundover an extended period of time to control infestation of the ruminantdomestic animals by arthropods.

Example 2L

A slow release composition in the form of granules, pellets, brickettesor the like can be prepared with compositions as follows:

-   -   Active ingredient 0.5 to 25%    -   Polyvinyl chloride 75 to 99.5%    -   Dioctyl phthalate (plasticizer)

The components are blended and then formed into suitable shapes bymelt-extrusion or molding. These composition are useful, for example,for addition to standing water or for fabrication into collars oreartags for attachment to domestic animals to control pests by slowrelease.

Example 2M

A water dispersible granule is prepared with the composition as follows:

Active ingredient    85%(max) Polyvinylpyrrolidone 5% Attapulgite clay6% Sodium lauryl sulfate 2% Glycerine 2%

The ingredients are mixed as a 45% slurry with water and wet milled to aparticle size of 4 microns, then spray-dried to remove water.

Methods of Pesticidal Use

The following representative test procedures, using compounds of theinvention, were conducted to determine the parasiticidal and pesticidalactivity of compounds of the invention.

Method A: Screening Method to Test Systemicity of Compounds AgainstCtenocephalides felis (Cat Flea)

A test container was filled with 10 adults of Ctenocephalides felis. Aglass cylinder was closed on one end with parafilm and placed on top ofthe test container. The test compound solution was then pipetted intobovine blood and added to the glass cylinder. The treatedCtenocephalides felis were held in this artificial dog test (blood 37°C., 40-60% relative humidity; Ctenocephalides felis 20-22° C., 40-60%relative humidity) and assessment performed at 24 and 48 hours afterapplication.

Compound numbers 1-2, 1-8, 1-9, 1-10, 1-14, 1-15, 1-16, 1-17, 1-19,1-34, 1-35, 1-36, 1-37, 1-38, 1-39, 1-40, 2-2, 2-8, 2-9, 2-10, 2-14,2-16, 2-17, 2-19, 2-35, 2-36 and 3-19 gave at least 90% control ofCtenocephalides felis at a test concentration of 5 ppm or less.

Method B: Diabrotica undecimpunctata (Southern Corn Rootworm) Screen

Two days before application, seeds of maize were soaked in water underwarm conditions to elicit fast germination. One day before application,eggs of Diabrotica undecimpunctata were transferred to one half of aJapanese filter paper placed in a plastic petri dish. Afterwards, asprouted maize seed was placed on a moistened pad beside the filterpaper. Three drops of 200 microlitres of test compound solution werecarefully pipetted onto the egg. The remainder of the solution wasplaced on the maize and then the Petri dish was closed. The treated eggsin the Petri dishes were held in a climate chamber for 6 days. Thecompound efficacy (percentage of dead eggs and/or larvae in comparisonto untreated control) was assessed 6 days after application using abinocular microscope.

Compound numbers 1-17 , 1-19, 1-35, 1-36, 1-38, 1-39, 2-9, 2-19, 2-35and 2-36 gave at least 90% control of Diabrotica undecimpunctata at atest concentration of 10 ppm.

Method C: Nephotettix Cinciceps (Rice Leafhopper) Screen

The leaves of 12 rice plants having a stem length of 8 cm were dippedfor 5 seconds into an aqueous solution of the formulated test compound.After the solution had run off, the rice plants treated in this mannerwere placed in a Petri dish and populated with about 20 larvae (L3stage) of Nephotettix cincticeps. The Petri dish was closed and thenstored in a climate chamber (16 hours of light/day, 25° C., 40-60%relative humidity). After 6 days storage, the percentage mortality ofleafhopper larvae was determined.

Compound numbers 1-8, 1-9, 1-19, 1-35, 1-37, 2-2, 2-8, 2-19 and 2-36gave at least 98% mortality of Nephotettix cinciceps larvae at a testconcentration of 100 ppm.

Method D: Screening Method to Test Contact Activity AgainstCtenocephalides felis (Cat Flea)

Solutions of the test compounds were dropped onto filter paper, driedand the filter paper placed into test tubes and infested with 10 adultsof Ctenocephalides felis. The treated Ctenocephalides felis were held ina climate chamber (26° C., 80% RH) and the percentage efficacy assessed24 hours and 48 hours after application in comparison with the untreatedcontrol.

Compound numbers 1-2, 8-2 and 8-10 gave at least 70% contact control ofCtenocephalides felis at a test concentration of 1000 ppm.

Method E: Screening Method to Test Contact Activity AgainstRhipicephalus sanguineus (Brown Dog Tick)

Solutions of the test compounds were dropped onto filter paper, driedand the filter paper placed into test tubes and infested with 20-30larvae (L1) of Rhipicephalus sanguineus and the tubes closed with aclip. The treated Rhipicephalus sanguineus were held in a climatechamber (25° C., 90% RH) and the percentage efficacy assessed 24 hoursafter application in comparison with the untreated control.

Compound numbers 1-2, 3-3, 8-8, 8-10 and 8-22 gave at least 70% contactcontrol of Rhipicephalus sanguineus at a test concentration of 100 ppm.

1. 5-Substituted-alkylaminopyrazole derivatives of formula (I):

wherein: R¹ is CN; W is C-halogen or C—CH₃; R² is hydrogen, halogen orCH₃; R³ is (C₁-C₃)-haloalkyl, (C₁-C₃)-haloalkoxy orS(O)_(p)—(C₁-C₃)-haloalkyl; R⁴ is hydrogen, (C₂-C₆)-alkenyl,(C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl,(C₃-C₇)-cycloalkyl, CO—(CH₂)_(q)—R⁷, CO₂R⁸, CO—(CH₂)_(q)R⁹,—CO—(C₁-C₄)-alkyl-(C₁-C₆)-alkoxy, —CO₂—(CH₂)_(q)R⁷, —CO₂—(CH₂)_(q)—R⁹,—CO₂—(C₃-C₇)-cycloalkyl, —CO₂—(C₁-C₄)-alkyl-(C₃-C₇)-cycloalkyl,—CO₂—(C₃-C₆)-alkenyl, —CO₂—(C₃-C₆)-alkynyl, CONR¹⁰R¹¹, —CH₂R⁷, —CH₂R⁹,OR⁷, OR⁸ or OR⁹; or (C₁-C₆)-alkyl which is substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)-alkoxy,(C₁-C₆)-haloalkoxy, (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CO₂—(C₁-C₆)-alkyl,—O(C═O)—(C₁-C₆)-alkyl, NR¹⁰COR¹², NR¹⁰R¹¹, CONR¹⁰R¹¹, SO₂NR¹⁰R¹¹, OH,CN, N₂, OR⁷, NR¹⁰SO₂R⁸, COR⁸ and OR⁹; A is (C₁-C₁₂)-alkylene andC₁-C₁₂)-haloalkylene in which 2, 3 or 4 adjacent carbon atoms optionallyform part of a (C₃-C₈)-cycloalkyl ring which is unsubstituted orsubstituted by one or more radicals selected from the group consistingof (C₁-C₆)-alkyl and halogen; R⁵ is H, (C₃-C₆)-alkenyl,(C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl, (C₃-C₆)-haloalkynyl,(C₃-C₇)-cycloalkyl, —(CH₂)_(q)R⁷, —(CH₂)_(q)R⁹ or NR¹⁰R¹¹ provided thatfor the last mentioned radical m is 2; or is (C₁-C₆)-alkyl unsubstitutedor substituted by one or more radicals selected from the groupconsisting of halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,(C₃-C₆)-alkenyloxy, (C₃-C₆)-haloalkenyloxy, (C₃-C₆)-alkynyloxy,(C₃-C₆)-haloalkynyloxy, (C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CN, NO₂, OH,COR¹⁰, NR¹⁰COR¹², NR¹⁰SO₂R⁸, CONR¹⁰R¹¹, NR¹⁰R¹¹, S(O)_(p)R⁷, S(O)_(p)R⁹,OR⁷, OR⁹ and CO₂R¹⁰; R⁶ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,(C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl or(C₂-C₆)-haloalkynyl; R⁷ is phenyl unsubstituted or substituted by one ormore radicals selected from the group consisting of halogen,(C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy,CN, NO₂, S(O)_(p)R⁸, COR¹¹, COR¹³, CONR¹⁰R¹¹, SO₂NR¹⁰ OR¹¹, NR¹⁰OR¹¹,OH, SO₃H and (C₁-C₆)-alkylideneimino; R⁸ is (C₁-C₆)-alkyl or(C₁-C₆)-haloalkyl; R⁹ is heterocyclyl unsubstituted or substituted byone or more radicals selected from the group consisting of halogen,(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,NO₂, CN, CO₂(C₁-C₆)-alkyl, S(O)_(p)R⁸, OH and oxo; R¹⁰ and R¹² are eachindependently H, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-alkenyl,(C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl, (C₃-C₆)-haloalkynyl,(C₃-C₆)-cycloalkyl, —(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl, —(CH₂)_(q)R¹³ or—(CH₂)_(q)R⁹; or R¹⁰ and R¹¹ and/or R¹⁰ and R¹² each together with therespective attached N atom form a five- or six-membered saturated ringwhich optionally contains an additional hetero atom in the ring which isselected from O, S and N the ring being unsubstituted or substituted byone or more radicals selected from the group consisting of halogen,(C₁-C₆)-alkyl and (C₁-C₆)-haloalkyl; R¹¹ and R¹⁴ are each independentlyH, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl or—(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl; R¹³ is phenyl unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy,(C₁-C₆)-haloalkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹¹R¹⁴; R¹⁵ is R¹¹ or—(CH₂)_(q)R¹³; m, n and p are each independently zero, one or two; q iszero or one; and each heterocyclyl in the above-mentioned radicals isindependently a heterocyclic radical having 3 to 7 ring atoms and 1, 2or 3 hetero atoms in the ring selected from the group consisting of N, Oand S; or a pesticidally acceptable salt thereof. 2.5-Substituted-alkylaminopyrazole derivatives of formula (I) as in claim1, or pesticidally acceptable salts thereof, wherein: R¹ is CN; W isC-halogen or C—CH₃; R² is hydrogen, halogen or CH₃; R³ is(C₁-C₃)-haloalkyl, (C₁-C₃)-haloalkoxy or S(O)_(p)—(C₁C₃)-haloalkyl; R⁴is hydrogen, (C₁-C₆)-alkyl or COR⁸; A is (C₁-C₁₂)-alkylene and(C₁-C₁₂)-haloalkylene in which 2, 3 or 4 adjacent carbon atomsoptionally form part of a (C₃-C₈)-cycloalkyl ring which is unsubstitutedor substituted by one or more radicals selected from the groupconsisting of (C₁-C₆)-alkyl and halogen; R⁵ is H, (C₃-C₆)-alkenyl,(C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl, (C₃-C₆)-haloalkynyl,(C₃-C₇)-cycloalkyl, —(CH₂)_(q)R⁷, —(CH₂)_(q)R⁹ or NR¹⁰R¹¹ provided thatfor the last mentioned radical S(O)_(m) is SO₂; or is (C₁-C₆)-alkylsubstituted by one or more radicals selected from the group consistingof halogen, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₃-C₆)-alkenyloxy,(C₃-C₆)-haloalkenyloxy, (C₃-C₆)-alkynyloxy, (C₃-C₆)-haloalkynyloxy,(C₃-C₇)-cycloalkyl, S(O)_(p)R⁸, CN, NO₂, OH, COR¹⁰, NR¹⁰COR¹²,NR¹⁰SO₂R⁸, CONR¹⁰R¹¹, NR¹⁰R¹¹, S(O)_(p)R⁷, S(O)_(p)R⁹, OR⁷, OR⁹ andCO₂R¹⁰; R⁶ is (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl,(C₂-C₆)-haloalkenyl, (C₂-C₆)-alkynyl or (C₂-C₆)-haloalkynyl; R⁷ isphenyl unsubstituted or substituted by one or more radicals selectedfrom the group consisting of halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,(C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, CN, NO₂, S(O)_(p)R⁸, COR¹¹, COR¹³,CONR¹⁰R¹¹, SO₂NR¹⁰R¹¹, NR¹⁰R¹¹, OH, SO₃H and C₁-C₆)-alkylideneimino; R⁸is (C₁-C₆)-alkyl or (C₁-C₆)-haloalkyl; R⁹ is heterocyclyl unsubstitutedor substituted by one or more radicals selected from the groupconsisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, NO₂, CN, CO₂(C₁-C₆)-alkyl, S(O)_(p)R⁸, OH and oxo;R¹⁰ and R¹² are each independently H, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,(C₃-C₆)-alkenyl, (C₃-C₆)-haloalkenyl, (C₃-C₆)-alkynyl,(C₃-C₆)haloalkynyl, (C₃-C₆)-cycloalkyl,—(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl, —(CH₂)_(q)R¹³ or CH₂)_(q)R⁹; or R¹⁰and R¹¹ and/or R¹⁰ and R¹² each together with the respective attached Natom form a five- or six-membered saturated ring which optionallycontains an additional hetero atom in the ring which is selected from O,S and N, the ring being unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₆)-alkyland (C₁-C₆)-haloalkyl; R¹¹ and R¹⁴ are each independently H,(C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl or—(C₁-C₆)-alkyl-(C₃-C₆)-cycloalkyl; R¹³ is phenyl unsubstituted orsubstituted by one or more radicals selected from the group consistingof halogen, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy,(C₁-C₆)-haloalkoxy, CN, NO₂, S(O)_(p)R⁸ and NR¹¹R¹⁴; R¹⁵ is R¹¹ or—(CH₂)_(q)R¹³; m, n and p are each independently zero, one or two; q iszero or one; and each heterocyclyl in the above-mentioned radicals isindependently a heterocyclic radical having 3 to 7 ring atoms and 1, 2or 3 hetero atoms in the ring selected from the group consisting of N, Oand S.
 3. 5-Substituted-alkylaminopyrazole derivatives of formula (I) asin claim 1, or pesticidally acceptable salts thereof, wherein thesymbols and indices in formula (I) have the following meanings: R¹ isCN; R² is chlorine; R³ is CF₃ or OCF₃; W is C—Cl; R⁴ is hydrogen or(C₁-C₆)-alkyl; R⁵ is (C₁-C₆)-alkyl; R⁶ is CF₃; A is (C₂-C₃)-alkylene andm and n are each independently zero, one or two.
 4. A pesticidalcomposition comprising a compound of formula (I) or a pesticidallyacceptable salt thereof as defined in any one of claims 1 to 3 inassociation with a pesticidally acceptable diluent or carrier and/orsurface active agent.